TW522593B - Non-aqueous electrolytic solution secondary battery - Google Patents

Abstract

The present invention provides a lithium-ion secondary battery whose power characteristic has been improved without widening a battery size. A cylindrical lithium-ion battery 20 accommodates a winding group 6 and a non-aqueous electrolytic solution within a battery container 7. The winding group 6 is structured by winding a positive electrode using lithium manganate (Li1+xMn2-xO4 or Li1+xMn2-x-yAlyO4) where an average particle diameter of primary particles is in a range of from 0.1 μm to 2 μm as a positive electrode active material and a negative electrode using amorphous carbon as a negative electrode active material via a separator. The reaction area of the positive electrode active material is optimized.

Description

522593 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the Invention (1) [Technical Field] The present invention relates to a non-aqueous electrolyte secondary battery, and particularly relates to a secondary particle that is formed from a primary particle aggregate. The positive electrode active material mixture of lithium fibrous complex oxide and conductive material composed of the secondary particles' applies this positive electrode active material. The material mixture is approximately uniformly and equally coated on the positive electrode on both sides of the belt-shaped current collector. And a negative electrode that can absorb and release ions through charge and discharge, and wound the positive electrode and the negative electrode through a separator to form an electrode winding group. 'This electrode winding group is stored in an internal pressure that is opened by a specific pressure. Non-aqueous electrolyte secondary battery in a battery container of the mechanism. [Known Technology] Lithium-ion secondary batteries, which represent non-aqueous electrolyte secondary batteries, have the advantage of high energy density. They are mainly used as power sources for belt-type equipment such as VTR cameras, notebook computers, and mobile phones. The internal structure of this battery is usually formed into a winding type as shown below. The electrodes are the positive electrode and the negative electrode, both of which are band-shaped, in which an active material is coated on a metal foil, and are wrapped with a separator, so that the cross-sections where the positive electrode and the negative electrode are not in direct contact are wound in a spiral shape to form a winding group. This winding group is stored in a cylindrical battery can forming a battery container, and after being filled with an electrolyte, it is sealed. The size of general cylindrical lithium ion secondary batteries is widely used as a small non-aqueous electrolyte secondary battery for civilian use, with a diameter of igmm and a height of 65mm. Carbon materials are generally used as the negative electrode active material of 1 86 5 0-type lithium ion secondary batteries. This carbon material can be made of natural graphite, flake-like, block-like artificial graphite, mesophase pitch-based stone 3 — ----------------------- ----- ^ (Please read the notes on the back before filling this page)

522593 V. Description of the invention (2 graphite-based materials such as ink 'and non-quality carbon materials sintered with furan alcohol and other cynan resins. The positive electrode active material generally uses lithium transition metal gas :: matter, where capacity or circulation From the viewpoint of balance such as characteristics, lithium cobaltate is widely used. The battery capacity of 1 8650 lithium ion secondary batteries is about 1.38-11 ~ 1.7811, and the output is about 1. Please. In addition, in the automotive industry In response to the issue of protection, we are accelerating the development of electric vehicles (EVs) with no exhaust gas as the power source and only battery-powered electric vehicles (EVs), and hybrid (electronic) vehicles (HEVs) with both internal combustion engine and batteries as power sources. The middle part has entered the practical stage. 彳 'To form a battery for electric vehicle power, of course, it is required to obtain high-wheel-out and high-energy characteristics. On batteries that meet this requirement, lithium ion secondary batteries have attracted much attention. In order to popularize electric vehicles, it is necessary to reduce the price of batteries. Therefore, low-cost battery materials are being sought. For example, in the case of a positive electrode active material, a rich oxide of money is used. It has attracted particular attention, and is aiming at improving the performance of batteries. However, the output characteristics of bell-ion primary batteries using violent complex oxide as a positive electrode active material may not necessarily be referred to as an electric vehicle. Enough. On the other hand, although the direction of increasing the capacity of the battery has been explored in order to expand the electrode area, if the battery size becomes larger, it will cause practical difficulties in consideration of the space of the vehicle. Also, in The battery for electric vehicles requires not only high capacity, but also high output such as acceleration performance, that is, lowering the internal impedance of the battery. In order to increase the electrode reaction area, if the positive electrode active material μ is set to have a larger specific surface area Li manganese complex oxide, you can correspond to this paper. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the matter on the back before filling out this page.) Order- ------- Printed by the Consumers' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 4-1 522593 Printed by the Consumers ’Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 V. Invention Description (3) Request. In terms of the specific surface area, the particle size of the lithium manganese complex oxide can be reduced by increasing the specific surface area. However, on the smaller particle size, the powder will be scattered and applied for coating when the electrode is produced. Disadvantages such as the difficulty of slurrying on the two sides of the electrode body. To improve this problem, it is necessary to aggregate primary particles with smaller particle sizes to form secondary particles, and then form secondary particles from them. The countermeasures of lithium manganese complex oxide. Furthermore, when the production of high-output non-aqueous electrolyte secondary batteries is dry, efforts are being made to reduce the reaction resistance between the positive electrode active material and the non-aqueous electrolyte. Techniques such as shortening the ion diffusion distance in the negative electrode to make the positive electrode and the negative electrode thin, or lengthening the positive electrode and the negative electrode in order to increase the physical reaction area of the positive electrode and the negative electrode. However, for electric vehicles, it is particularly used in the case of HEV. Because larger output characteristics are required, in the above-mentioned technology for thinning and growing the positive and negative electrodes, the space in the battery will be occupied by parts other than the positive electrode active material, making the positive electrode active material in the battery Occupancy area is reduced, thereby reducing the amount of filler must be a positive electrode active substance. This means that the load of the average positive electrode active material will increase. “The meaning is at the time of charging and discharging at a high rate of pulsed current.” This is especially because lithium ions will temporarily concentrate on the positive electrode activity during discharge. On the surface of the material, it is usually difficult to insert the via ion at the part of the reaction end, and the load on the positive electrode active material will also increase. Therefore, if the pulse charge / discharge cycle is repeatedly performed for a long period of time, the structure of the positive electrode active material will be destroyed with the overvoltage, and a problem that the output will be greatly reduced will occur. Furthermore, in the case of lithium-ion secondary batteries, the higher the capacity of the paper, the larger the paper size will apply to the Chinese national standard (χ 297 meals). 1 5- ------------------ -Order · -------- Line 7 (Please read the precautions on the back before filling out this page) 522593 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (4) Quantity, high When outputting, 'the more the security tends to decrease. In particular, as described above, in a non-aqueous electrolyte secondary battery aiming at high output, it has been found that the battery tends to have a slightly fierce phenomenon when it enters an abnormal state. In other words, in the reaction when the lithium ion secondary battery is overcharged, all lithium ions are desorbed from the positive electrode active material, and even the structure becomes unstable with overvoltage, and the non-aqueous electrolyte is more easily decomposed. . When the non-aqueous electrolyte is decomposed, at the interface where the lithium-manganese complex oxide, which is a positive electrode active material, comes into contact with the non-aqueous electrolyte, a deoxidation reaction will be initiated along with the decomposition of the non-aqueous electrolyte. When the particles of lithium manganese complex oxide are smaller, the average unit volume area of lithium manganese complex oxide and non-aqueous electrolyte will increase, and the deoxidation reaction will increase, so the smaller particles will be generated The heat dissipation from structural destruction will promote the structural destruction of adjacent particles, leading to the heat dissipation of chain structural destruction, and reaching the energy level of the overall cathode active material structural destruction, and the problem of white smoke caused by battery heat dissipation or internal pressure opening mechanism. High-capacity, high-output batteries used in power sources for electric vehicles usually have high current charging and high current discharge when the battery is abnormal. As commonly used in 18650 lithium-ion batteries, they will fit inside the battery when the battery is abnormal. It is difficult to install a current blocking mechanism (a cut-off switch) that operates when the voltage rises inside the battery structure. In the case of an electric vehicle for people to ride, the battery must be secured at least as far as possible, such as overcharging when the charging control system fails, crushing that can occur in an accidental collision, or external short circuit caused by puncture by a foreign object. For its own safety, this is a very important battery characteristic. In addition, all paper sizes are subject to the Chinese National Standard (cns) a4 (210 X 297 g t) ------------ i -------- Order ----- ---- Line 『(Please read the 4 items on the back before filling out this page) -6- Printed by the Intellectual Property Bureau Employee Consumer Cooperative of the Ministry of Economy 522593 A7 —------------ B7_____ 5 5. Description of the invention (5) The safety of the battery means that when the battery is in an abnormal state, any movement of the battery will certainly not cause damage to the human body, and the damage to the vehicle can be suppressed to the minimum. [Invention] In view of the above facts, the first object of the present invention is to provide a non-aqueous electrolyte secondary battery that is not sized and has improved output characteristics. The second object of the present invention is to provide a high capacity, high Non-aqueous electrolyte secondary battery with high energy density, high output, and high safety. Furthermore, a second object of the present invention is to provide a non-aqueous electrolyte secondary battery which can maintain a high output even if the pulse charge / discharge cycle is repeated for a long period of time. 1_Yuan, in order to achieve the above-mentioned first object, the present invention is characterized in that it comprises a lithium manganese complex oxide composed of a primary particle aggregate, and a secondary electrode composed of the secondary particle and a positive electrode active material of a conductive material. This positive electrode active material mixture is applied to the positive electrode coated on both sides of the belt-shaped current collector approximately uniformly and in an equal amount, and the negative electrode capable of absorbing and releasing lithium ions through charge and discharge. The positive electrode and the negative electrode are rolled through a separator. A non-aqueous electrolyte secondary battery in which an electrode winding is formed, and the electrode winding group is stored in a battery container having an internal pressure opening mechanism for opening the internal pressure by using a specific pressure; The average particle diameter of the primary particles of the material is 0. 1 μηι ~ 2 μιτι 〇) In the present invention, if the positive electrode active material uses a lithium manganese complex oxide having an average primary particle diameter of less than 0.1, the reaction area is It will increase, but because the crystal cannot grow sufficiently, the paper size of the paper that will cause the reaction impedance is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 meals) a 7 ------------- -------- Order ------ --- Line "(Please read the unintentional matter on the back before filling in this page) 522593 A7 V. Description of the invention (6) Increase and decrease the output of non-aqueous electrolyte secondary battery; otherwise, if the primary particles are used If the average particle size exceeds 2 μm of lithium manganese complex oxide, the reaction area will be reduced, and the current density of the average positive electrode active material will be increased. Therefore, the output of the non-aqueous electrolyte secondary battery will be reduced < Lithium-manganese complex oxides with an average primary particle size of 1 μm or more and 2 μm or less can be used to obtain a non-aqueous solution that optimizes the reaction area of the positive electrode active material and can improve the wheel-out characteristics without increasing the battery size. Electrolyte secondary battery). In this case, if a fibrous complex oxide with a Li / Mn composition ratio in the range of 0.55 or more and 0.60 or less is used, compared with the theoretical composition (Li / Mn = 0.5), there is no extreme reduction in discharge capacity, and the amount of manganese dissolution can be reduced. In this type of lithium manganese complex oxide, it is best to use the chemical formula

Li1 + xMn2_x〇4, or a part of manganese in the chemical formula is replaced with other metal elements. Furthermore, in order to achieve the above-mentioned second object, the present invention is that the lithium manganese complex oxide has an average single-side coating amount of the electrode body in a range of 80 g / m2 to 160 g / m2, and the positive electrode active material is active. The amount of conductive material contained in the agent is in the range of 8 wt% to 16 wt%, or the average single-side coating amount of the electrode body of the lithium manganese complex oxide is in the range of 270 g / m2 to 3 3 0 g / m2, and the The amount of the conductive material contained in the positive electrode active material active agent ranges from 3% to 7% by weight. In a two-capacity, high-output non-aqueous electrolyte secondary battery, when trapped in an abnormal state, a high-current charge or high-current discharge state is maintained, and the chemical reaction between the non-aqueous electrolyte and the active substance activator is in the battery container. This paper size is applicable to Chinese National Standard (CNS) A4 specification (210 X 297 g t). (Read Qi Ai's urgent matters on the back before filling out this page) -------- Order ------- -Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 8 — Printed by the Consumer ’s Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 522593 V. Description of the invention (7) The gas will be generated sharply and in large quantities, causing the internal pressure of the battery container to rise . (Generally speaking, in a non-aqueous electrolyte secondary battery, to prevent the internal pressure in the battery container from rising, "the battery container is provided with an internal pressure opening mechanism that opens the internal pressure at a specific pressure. The average coating amount of the early surface of the oxide is in the range of 80 g / m2 to 16 g / m2, and the amount of the conductive material contained in the positive electrode active material active agent is in the range of 8% to 16% by weight, or lithium The average manganese complex oxide single-side coating amount is in the range of 270 g / m2 to 330 g / m2, and the amount of the conductive material contained in the positive electrode active material active agent is in the range of 3% to 7% by weight. Extremely stable execution of gas release from the internal pressure opening mechanism; therefore, according to the present invention, 'not only high capacity, high output, and non-aqueous electrolyte secondary batteries with extremely high safety can be achieved in this case' If graphite and amorphous carbon are used in the conductive material, a non-aqueous electrolyte secondary battery with higher output can be formed. At this time, if the average particle diameter of graphite is set to the average particle diameter of secondary particles @ 〇2 times ~ Times and / or amorphous carbon with acetylene black Non-aqueous electrolyte secondary battery with higher output. In addition, if the Li / Mn composition ratio of the Zhongye emulsion is set in the range of G 55 ~ Q 6 (), it will not decrease with the capacity, and the output can be improved. Maintenance rate. In addition, if amorphous carbon is used as the negative electrode active material, a non-aqueous electrolyte secondary battery with high capacity and better safety can be formed.) Wang Zai, in order to achieve the above-mentioned second objective, also Can use the chemical formula Lll + xMn2.x〇4 'or some of the chemical formula and other metal elements to replace or doped _ multiple oxides, and the fluorene oxygen table paper size applies Chinese national standards (CNS ) A4 Specification (210 X 297 Meal One 9 ----------- ^ J -------- Order --------- Line 7 (Please read the first on the back Note: Please fill in this page again.) 522593 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 Β7 V. Description of the invention (8) The particle weight of the compound with a particle size of 1 μm or less is set to 〇1 ❶ / ❶ or less. According to this , Because it can reduce the interfacial area per unit area of lithium manganese complex oxide and non-aqueous electrolyte, and reduce the deoxidation reaction The heat is dissipated, so the chain reaction between the positive electrode active material and the non-aqueous electrolyte can be suppressed. Therefore, not only a high energy density and high output can be formed, but also a non-aqueous electrolyte secondary battery with excellent safety can be realized.! In this case, By setting the specific surface area of the positive electrode active material to 0.6 m2 / g or less, the area of the interface between the positive electrode active material and the non-aqueous electrolyte can be reduced, and chain reactions can be suppressed. Therefore, non-aqueous electrolysis with superior safety can be obtained. Liquid secondary batteries. Then, in order to achieve the third object described above, the present invention is characterized by using lithium represented by the chemical formula Li1 + xMn2-x〇4, or a part of the manganese in the chemical formula is replaced or doped with lithium by other metal elements. The weight of the particles of manganese complex oxide and lithium manganese complex oxide is 1 μm or less, in the range of 0.001% to 2%. In the present invention, by setting the weight of the particles having a particle diameter of the positive electrode active material to 0.01% or more and particles having a particle diameter of 1 μm or less, the non-aqueous electrolyte can be filled around and uniformly wetted in the non-aqueous electrolyte. In the liquid. Therefore, even if a long-term pulse charge-discharge cycle is performed, since lithium ions are smoothly inserted into the positive electrode active material, it is judged that the discharge reaction can be easily performed, and no structural damage is caused without generating a voltage difference in the positive electrode active material. As described above, the effect of reducing the discharge load applied to the entire positive electrode can be expected for particles having a particle size of one or less. In addition, if the weight of the positive electrode active material is less than 1% and the particle weight is more than 2%, the adhesion between the positive electrode active materials will be weakened. In the long-term pulse charge and discharge cycle, the positive electrode active material will be used by the positive electrode in the paper size of China. National Standard (CNS) A4 Specification (210 X 297 Meals) -------------------- IT --------- ^ ΦΓ (Please first Read the note t on the back and fill in this page) -10- 522593 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention description (9 The result will lead to a reduction in output ', so the particle size of the positive electrode active material must be The weight of the following particles is set to less than 2%. According to the present invention, by setting the weight of the particles having a plate diameter of 1 μm or less of the positive electrode active material to 0.01% to 2%, even if the pulse charge and discharge cycle is repeated for a long time, it can be obtained Maintain a high output non-aqueous electrolyte secondary battery. In this case, even if the specific surface area of the positive electrode active material is set to more than 0 6m2 / CT, the reaction area can be increased and the discharge reaction can be performed. The effect of the discharge load on the overall positive electrode. If the specific surface area is greater than 2.0m2 / g, the elution amount of manganese ions maintained at a high temperature will increase, making it difficult for current to flow, and reducing output due to reduced capacity. Therefore, it is best to set the specific surface area of the positive electrode active material 0.6m2 / g to 2.0m2 / g. [Simplified description of the drawing] Fig. 1 is a schematic cross-sectional view of a cylindrical lithium-ion battery using a first embodiment of the present invention. Fig. 2 is a drawing using the first Sectional schematic diagram of a cylindrical lithium-ion battery in the second embodiment. [Detailed description of the preferred embodiment] (First embodiment) Below, please refer to the diagram for the secondary non-aqueous electrolyte of the present invention. The battery will be described in the first embodiment of a cylindrical lithium-ion battery for HEV. (Positive electrode) As shown in Figure 1, the national acid (CNS) A4 specification is applied to the acidic material of the positive electrode active material according to the paper standard. (210 X 297 public meals) ------ --Order ------- line τ (Please read the > I matter on the back before filling in this page) 11- 522593 Employees ’Consumption of Intellectual Property, Ministry of Economic Affairs A7 printed by the cooperative 10) Back-end technology of powder and conductive materials 2Shanji # 七 丨 inch W, special adhesive, polyvinylidene fluoride (PVDF) of adhesive 'Enter into ^ σ according to specific mixing ratio and add dispersion in it> ; N-methyl of cereals, 2-% kappa / ΤνΤ IV yf Γ >, pyrrolidone (NMP), kneaded to form a slurry. This material was then applied to ^ 户 # Λ Κ On the two sides of the aluminum foil W1 (positive electrode body L) with a thickness of 20 μm, Ye Tushi left an uncoated portion with a width of 30 mm on one side edge of the positive electrode plate in the longitudinal direction. After drying, stamping, and cutting ^, a positive electrode plate with a specific thickness of 82_ and a specific length of active material mixture can be obtained. The bulk density of the positive electrode active material mixture layer W2 is set to 2.65 g / cm3. A notch is provided in the above-mentioned uncoated portion, and the remaining portion where no notch is provided is used as the positive electrode conductive sheet 2. The phase positive electrode conductive sheet 2 is set to 50_interval 'and the width of the positive electrode conductive sheet 2 is set to 5 mm. (Negative electrode) To 92 parts by mass of the specific carbon powder, 8 parts by mass of polyvinylidene fluoride was added, and a dispersion solvent of N-methyl · 2 · pyrrolidone was added thereto to form a slurry after kneading. This slurry was applied on both sides of a thickness i and rolled copper 羯 W3 (negative electrode current collector). At this time, an uncoated portion having a width of 30 mm was left on the side edge of the negative electrode plate. After drying, stamping and cutting, a negative electrode with a specific thickness of 86 mm in width and a specific length of the active material coating portion was obtained. The negative electrode plate was compressed to give a negative electrode active material mixture layer W4 with a porosity of about 35%. In the above eight uncoated portions, notches are provided in the same manner, and the remaining portion without the notches is used as the negative electrode conductive sheet 3. Adjacent negative electrode conductive sheets 3 were set to 50 mm intervals, and the width of the negative electrode conductive sheets 3 was set to 5 mm. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm ----------- ^ -------- order --------- line Γ (Please read the precautions on the back before filling in this page) • 12 — 522593 A7 V. Description of the invention (η (battery making) Put the positive and negative plates prepared above into contact with the two plates without touching them. It is wound together with a polyethylene separator W5 with a width of 90 mm and a thickness of 40 μm. At the winding center, a hollow cylindrical shaft core 1 made of polypropylene is used. Trap τ & At this time, the positive electrode conductive sheet 2 and the negative electrode conductive sheet 3 are respectively located at the end positions of the two opposite ends of the winding group 6. In addition, the length of the negative electrode plate and the separator is adjusted, and the diameter of the winding group is set to 3 8 soil 0.1 mm. " Deform the positive electrode conductive sheet 2 and make it all gather and contact the periphery of the positive electrode current collecting ring $ which extends from the winding core 6 axis core 1 to the vicinity of the flange wall surface protruding integrally, and then The positive electrode conductive sheet 2 and the flange wall surface are ultrasonically welded to connect the positive electrode conductive sheet 2 to the flange wall surface. In addition, the negative electrode current collector 5 The connection operation of the negative electrode conductive sheet 3 is also performed in the same manner as the connection between the positive electrode current collector ring 4 and the positive electrode conductive sheet 2. Then, 'the insulation coating is applied on the entire periphery of the flange wall surface of the positive electrode collector ring 4. This insulation coating The base material is polyimide, and one side is coated with an adhesive tape coated with an adhesive made of hexamethacrylate. This adhesive tape is wound from the flange wall surface along the winding group 6 The outer wall is wound with more than one layer to form an insulating coating, and the winding group 6 is inserted into a stainless steel battery container 7 which is plated with nickel. The outer diameter of the battery valley device 7 is 40 mm and the inner diameter is 39 mm. 5, the negative electrode guide plate 8 for conducting electricity is welded in advance, and then the winding group 6 is inserted into the battery container 7, and then the private paper size is applicable to the Chinese National Standard (CNS) A4 specification (21 × 297 mm) Please read the phonetic notes on the back before filling out this page) -------- Order --------- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-13 Printed by the cooperative 522593 A7 --------------- E___________ V. Description of the invention (12) The bottom of the battery container 7 and the negative electrode guide plate 8 are welded. In addition, in the positive current collecting ring 4, the top of the μ mountain top is not welded and is composed of a plurality of aluminum inscriptions T re-registered. The positive electrode guide 9 and the other end of the positive electrode guide 9 are 'fused to the underside of the battery cover for sealing the battery container 7. The battery cover is provided with a cylindrical lithium-ion battery 20 where the internal pressure rises.' The cracking valve u of the cracked internal pressure opening mechanism. The cracking pressure of the cracking width u is set to about 9 × 105 Pa. The battery cover is composed of a cover case ^, a cap body 13, a valve pushing portion 14 which maintains airtightness, and a cleavage valve?. These are laminated, and the periphery of the lid box body 12 is assembled with caulking. After the non-aqueous electrolyte is poured into a specific amount of the battery container 7, the positive electrode guide 9 is folded, and the battery container 7 is covered with a battery cover, and sealed with a 10-gauge EPDM resin airlock. Thereby, the cylindrical bell ion battery 20 is completed. In a non-aqueous electrolyte solution, lithium hexafluoride phosphate (LiPF6) is dissolved into 1 mole in a mixed solution of a volume ratio of 1: 1, of ethylene carbonate, dimethyl carbonate, and diethyl carbonate. Ear / liter In addition, the cylindrical lithium ion battery 20 is not provided with a current blocking or reducing mechanism such as a PTC (Positive Temperature Coefficient) element that operates as the battery temperature rises. Next, an example of a cylindrical lithium ion battery 20 obtained in accordance with this embodiment will be described. A battery of a comparative example produced for comparison is also described. (Example 1 -1) As shown in Table 1 below, in Example 1 -1, the paper size of the positive electrode active material was applied to the Chinese National Standard (CNS) A4 gauge (210 X 297 mm) ---- ------------- Order --------- Line, (Please read the first notice on the back before filling out this page) -14- 522593 A7 B7 ___ V. Invention Note (13) quality lithium manganate (LiMn204) powder with a primary particle size of about 1 to 2 μm, a secondary particle size of about 20 μm, and a Li to Mn atomic ratio (Li / Mn ratio) of 0.52, and the average particle size The flaky graphite with a diameter of 18 μηι and polyvinylidene fluoride were set at a weight ratio of 8 3: 1 2: 5 and the average collection of the positive electrode active material mixture layer (active material coating portion) W2 The coating amount of lithium manganate on one side of the electrical body was set to 80 g / m2, the thickness of the positive electrode active material mixture layer (active material coating portion) W2 (excluding the thickness of the current collector) was set to 73 μm, and the length of the positive electrode plate was set. Set it to 434cm. The average particle size of the flaky graphite was 0.9 times the primary particle size of LiMn204. In addition, in the negative electrode, the MCBM of the mesophase spherical graphite is used as the negative electrode active material, and the thickness of the negative electrode active material mixture layer (active material coating part) W4 (excluding the thickness of the current collector) is set to 53 μηι and the length is 446 cm. . The average particle size of the flaky graphite can be adjusted by screening. (Please read the notes on the back before filling out this page) Will order --------- Online wins 1 Printed on paper standards of the Ministry of Economic Affairs and Intellectual Property Bureau, Consumer Cooperatives, this paper applies the Zhongguanjia Standard (CNS) A4 Specifications_ (21G x 297 meals -15-522593 AT B7 V. Description of the invention (14 v〇hr! LD, ^ r jm lH m?:?:

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V. Description of the invention (15) In addition, when the electrode plate is wound, the positive electrode plate does not protrude from the negative electrode plate in the winding direction according to the innermost winding of the winding, and even in the outermost ring Where the positive electrode plate does not protrude from the negative electrode plate in the winding direction, 'the length of the negative electrode plate is set to be 12 cm longer than the length of the positive electrode plate. In addition, even in the winding direction and the vertical direction, the width of the negative electrode active material mixture layer W4 is larger than that of the positive electrode active material mixture layer W2 in such a manner that the positive electrode active material mixture layer W2 does not protrude from the negative electrode active material mixture layer W4. The width exceeds 4 mm (the same applies to the following examples and comparative examples). (Example 1-2) As shown in Table 1, in Example 1-2, in addition to setting the coating amount of lithium manganate to 120 g / m2, the positive electrode active material mixture (active material coating portion ) The thickness of W2 (excluding the thickness of the current collector) is set to 10 μm, the length of the positive electrode plate is set to 342 cm, the thickness of the negative electrode active material mixture (active material coating portion) is W4 (the thickness of the current collector is not included) is set to 79 μm, The length of the negative electrode plate was set to 3 54 cm, and the rest were made in the same manner as in Example υ. (Examples 1-2-2 to 1-2-5) As shown in Table 1, in Examples 1-2_2 to 1-2 · 5, the Li / Mn ratio of lithium manganate was set separately except that Except for 55, 0.58, 060, and 0.61, the rest were fabricated as in Example 1-2. (Example 1-3) As shown in Table 1, in Example 丨, except that the coating amount of lithium manganate was set to 160 g / m2, and the thickness of the positive electrode active material mixture (active material coating portion) W2 was ( The thickness of the collector is not included) is set to 146 μm, and the length of the positive electrode plate is set to 282 cm. 'Negative electrode active material mixture (active material coating This paper is applicable to China National Standard (CNS) A4 specifications (210 X 297 meals)] (Please read first Please fill in this page on the back of the matter.) -------- Order ------ 、 — Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 522593 Δ7 ---- " -------- __________ V. Description of the Invention (Part 16) W4 thickness (excluding the thickness of the current collector) is set to 106 μm, the length of the negative plate Except for the case of 294 cm, the rest were produced in the same manner as in the example. (Examples 1 to 4) As shown in Table 1, in Examples 1 to 4, the lithium manganate powder as in Example 1 to 1 was mixed with flaky graphite (relative to UMkO4 secondary particles) having an average particle diameter of 18 μm. Diameter flaky graphite average particle diameter: 0.9 times), and polyvinylidene fluoride, setting the blending ratio to 87: 8: 5 by weight%, and coating the positive electrode / tongue material mixture layer (active material coating) Part) The average coating amount of lithium manganate on one side of W2 is 120 g / m2, and the thickness of the positive electrode active material mixture layer (active material coating part) W2 (excluding the thickness of the current collector) is set The length was 104 μm, and the length of the positive electrode plate was set to 348 cm. In the negative electrode, MCBM was used as the negative electrode active material, and the thickness of the negative electrode active material mixture layer (active material coating part) W4 (excluding the thickness of the current collector) was set to 79 μm and the length was 360 cm to make a battery. (Example 1-5) As shown in Table 1, in the examples, the lithium manganate powder of the example was mixed with flaky graphite having an average particle diameter of 18 μm (relative to the flaky shape of the secondary particle diameter of LiMn204). Graphite average particle size: 009 times), and polyvinylidene fluoride, the blending ratio was set to 7 9: 1 6 ·· 5 by weight%, and the positive electrode active material mixture layer (active material coating portion) W2 The average coating amount of lithium manganate on one side of the current collector was 120 g / m2, and the thickness of the positive electrode active material mixture layer (active material coating portion) W 2 (excluding the thickness of the current collector) was 115 μm. , And the length of the positive electrode plate is set to 336 crn. In addition, in the negative electrode, the negative electrode active material uses MCBM, and the paper size of the negative electrode applies the Chinese National Standard (CNS) A4 specification (210 X 297 meals) ------------- (please first Read on the back; please fill in this page for further information.) Tr --------- ~ 18 522593 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 Description of the invention (17) Active substance mixture layer (active substance The thickness of the coating part (W4) (excluding the thickness of the current collector) was set to 79 μm and the length was 348 cm to prepare a battery. (Examples 1 to 6) As shown in Table 1, in Examples 1 to 6, fibrous acid powder as in Example b 1 and flaky graphite (relative to L i M π) having an average particle diameter of 18 μm were used. The average particle size of flaky graphite of 2 0 4 primary particle size: 0.9 times), and graphitized carbon black (KB), and polyvinylidene fluoride, the blending ratio is set to 8% by weight: 3 3: 1 0: 2: 5, and setting the average amount of lithium manganate coating on one side of the current collector of the positive electrode active material mixture layer (active material coating section) W2 to 120 g / m2, and coating the positive electrode active material mixture layer (active material coating) Section) The thickness of W2 (excluding the thickness of the current collector) is set to 10 μm, and the length of the positive electrode plate is set to 342 cm. In addition, in the negative electrode, MCBM was used as the negative electrode active material, and the thickness of the negative electrode active material mixture layer (active material coating part) W4 (excluding the thickness of the current collector) was set to 79 μm and the length was 3 54 cm to prepare a battery. (Example 1-7) As shown in Table 1, in Examples 1-7, the acid powder of Example ii was mixed with flaky graphite (relative to the secondary particle diameter of LiMn2O4) with an average particle diameter of 2 μm. Average particle size of flaky graphite: 〇 丨 times), with graphitized carbon black (KB), and polyvinylidene fluoride, the blending ratio is set to 83: 10: 2: 5 by weight%, and the positive electrode active material is The mixture layer (active material coating section) has an average lithium manganate coating amount of 120 g / m on one side of the current collector, and the thickness of the positive electrode active material mixture layer (active material coating section) w] is not included. Current collector thickness) is set to 109μΙΤ1, and the length of the positive plate is applied to the Chinese National Standard (CNS) A4 specification (210 X 297 g t). 19- (please note the notes on the back of Mtf before filling in this Page) > · n I— I— n · II ϋ m Γ., I nm βϋ «ni ·· — 11 n _ 522593 Printed by the Consumers’ Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (18) Set to 3 4 2 cm. In addition, in the negative electrode, a battery was fabricated by using M C B M ′ and setting the thickness of the negative electrode active material mixture layer (active material coating portion) w 4 (excluding the thickness of the current collector) to 79 μm and the length of 354 Cm. (Example 1-8) As shown in Table 1, in Examples 1 to 8, the lithium manganate powder as in Example 1 · i was mixed with flaky graphite (relative to LiMn2 04 2) with an average particle diameter of 4 μm. Average particle size of flaky graphite of secondary particle size: 0.2 times), graphitized carbon black (KB), and polyvinylidene fluoride. Set the blending ratio to 83: 10: 2: 5 by weight. The average active material mixture layer (active material coating portion) of the positive electrode active material mixture layer W2 has an average amount of lithium manganate coating on one surface of 120 g / m, and the positive electrode active material mixture layer (active material coating portion) w The thickness of $ (excluding the thickness of the current collector) is set to 109 μm, and the length of the positive electrode plate is set to 342 cm. In addition, in the negative electrode, MCBM was used as the negative electrode active material, and the thickness of the negative electrode active material mixture layer (active material coating part) W4 (excluding the thickness of the current collector) was set to 79 μηη and the length was 3 54 cm to prepare a battery. (Example 1-9) As shown in Table 1, in Example 丨 · 9, the rhenium acid powder of Example 1 q was mixed with flaky graphite (relative to LiMn2O4) having an average particle size of 1 μm Average particle size of flaky graphite of secondary particle size: 0.5 times), and graphitized carbon black (KB) 'and polyvinylidene fluoride, set the blending ratio to 83: 10: 2: 5 by weight%, and Set the average coating amount of lithium manganate on one side of the current collector of the positive electrode active material mixture layer (active material coating part) W2 as the paper standard applicable to China National Standard (CNS) A4 (210 X 297 g)- 2 0 ~ (Please read the notes on the back before filling in this page)

522593 A7 B7 Printed by the Consumer Cooperatives, Bureau of Intellectual Property, Ministry of Economic Affairs 5. Description of the invention (19) 120g / m2, set the thickness of the positive electrode active material mixture layer (active material coating part) W2 (excluding the thickness of the current collector) to 1 〇9μηη, and the length of the positive electrode plate was set to 342 cm. In the negative electrode, MCBM was used as the negative electrode active material, and the thickness of the negative electrode active material mixture layer (active material coating portion) W4 (excluding the thickness of the current collector) was set to 79 μm and the length was 354 cm to prepare a battery. (Example 1-10) As shown in Table 1, in Example 1-10, the lithium manganate powder of Example 1-1 was mixed with flaky graphite (relative to Li i) having an average particle diameter of 6 μm. Μ η2 〇4 The average particle size of flaky graphite once controlled: $, and graphitized carbon black (KB), and polyvinylidene fluoride. The compounding ratio is set to ΐ% 8 8: 1 0: 2 : 5 ', and set the average amount of lithium manganate coating on one side of the current collector of the positive electrode active material mixture layer (active material coating section) W2 to 120 g / m2, and set the positive electrode active material mixture layer (active material coating section) The thickness (excluding the thickness of the current collector) is set to 109 μm, and the length of the positive electrode plate is set to 342 cm. In addition, in the negative electrode, MCBM is used as the negative electrode active material, and the negative electrode active material mixture layer (active material coating portion) ) The thickness (excluding the thickness of the current collector) was set to 79 μm and the length was 354 cm. (Example 1 -1 1) As shown in Table 1, in Example 丨 _ i, it will be the same as Example 1 -1 lithium manganate powder, and flaky graphite with an average particle size of 10 μm (relative to UMn204 secondary particle size flakes Average graphite particle diameter: 0.5 times), with acetylene carbon black (ΑΒ), and polyvinylidene fluoride, the mixing ratio is set to be heavy (please read the intention on the back before filling this page) --- --------------. 21 — 522593 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (20) 篁% is 83 ·· 1〇 ·· 2_ · 5. Set the positive electrode active material mixture layer (active material 乂 cloth. 卩) to an average current collector coating amount on one side of V / 2 of 120 g / m2, and apply the positive electrode active material mixture layer (active material coating). The thickness of the cloth part (excluding the thickness of the current collector) is set to 109 μm, and the length of the positive electrode plate is set to 342 cm. In addition, in the negative electrode, MCBM is used as the negative electrode active material, and the negative electrode active material mixture layer (active material coating) is used. The thickness of the cloth part (excluding the thickness of the current collector) was set to 79 pm and the length was 3 54 cm. (Example 1-12) As shown in Table 1, in Example 丨 -12, the positive electrode active material was Lithium manganate (LiMn204) having a primary particle size of about 1 to 2 μm, a secondary particle size of about 20 μm, and an atomic ratio (Li / Mn ratio) of u to Mn of 0.55 ) Powder, with flaky graphite with an average particle size of 10 μm (relative to the average particle size of flaky graphite with a secondary particle size of LiMn204: 0.5 times), with acetylene black (AB), and polyvinylidene fluoride 'Set the blending ratio to 8 3 j 〇: 2: 5 by weight%, and set the average lithium acid coating amount on one side of the current collector of the positive electrode active material mixture layer (active material coating portion) W to 12 0 g / m2, the thickness of the positive electrode active material mixture layer (active material coating portion) W2 (excluding the thickness of the current collector) was set to 109 μm, and the length of the positive electrode plate was set to 342 cm. In addition, in the negative electrode, MCBM was used as the negative electrode active material, and the thickness of the negative electrode active material mixture layer (active material coating portion) W4 (excluding the thickness of the current collector) was set to 79 μm, and the length was 3 5 4 cm to produce a battery. (Example 1-13) As shown in Table 1, in Example 丨-丨 3, the positive electrode active material (please read the back of the page; i) and fill in this page)-Order ----- ----. This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297g t)

522593 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (21) Qualitative-secondary particle size of about 1 ~ 2μπι, secondary particle diameter of about 20μπι, and Li to Mn atomic ratio (Li / Mn ratio) 0.58 lithium manganate (LiMn204) powder, flaky graphite with an average particle size of 10 μm (average flaky graphite with secondary particle size of LiMn204: 0.5 times), and acetylene carbon black (AB), And polyvinylidene fluoride, the blending ratio is set to 8 3 ·· 10: 2: 5 by weight%, and the average current collector on one side of the positive electrode active material mixture layer (active material coating portion) W 2 is The coating amount of lithium manganate was 120 g / m2, the thickness of the positive electrode active material mixture layer (active material coating portion) W2 (excluding the thickness of the current collector) was 109 μm, and the length of the positive electrode plate was 342 cm. . In addition, in the negative electrode, MCBM was used as the negative electrode active material, and the thickness of the negative electrode active material mixture layer (active material coating portion) W4 (excluding the thickness of the current collector) was set to 79 μm and the length was 354 cm to prepare a battery. (Example 1-14) As shown in Table 1, in Example ^ 4, the primary particle diameter of the positive electrode active material was about 1 to 2 μm, the secondary particle diameter was about 20 μm, and the atomic ratio of Li to Mn (Li / Mn ratio) 0.60 lithium manganate (LiMn204) powder, flaky graphite with an average particle size of 10 μm (average flaky graphite with secondary particle size of LiMn2O4: 0.5 times), and acetylene Carbon black (AB) and polyvinylidene fluoride, the blending ratio is set to be 8% by weight: 3 3: [0: 2 · $, and the average current collection of the positive electrode active material mixture layer (active material coating portion) W2 is The amount of coated acid on one side of the body was set to 120 g / m2, the thickness of the positive electrode active material mixture layer (active material coating portion) W2 (excluding the thickness of the current collector) was set to 109 μm, and the positive electrode plate The length is set to 342 cm. In addition, in the negative electrode, MCBM is used as the negative electrode active material, and the negative electrode (please read the back of the book first; then fill in the cover sheet) fee ----- order ---------. This paper Standards apply to China National Standard (CNS) A4 specifications (210 X 297 public love)-23- 522593 Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (22) Active material mixture layer (active material coating department ) The thickness of W4 (excluding the thickness of the current collector) was set to 79 μm, and the length was 3 5 4 cm to make a battery. (Example 1-15) As shown in Table 1, in Examples 1-15, the primary particle diameter of the positive electrode active material was about 1 to 2 μm, the secondary particle diameter was about 20 μm, and the atomic ratio of Li to Mn (Li / Mri ratio) 0.61 lithium manganate (LiMn204) powder, flaky graphite with an average particle size of 10 μm (average flaky graphite with a secondary particle size of LiMn204, 0.5 times), and acetylene carbon black (AB), and 1 part of a mess of ethylene, the blending ratio is set to be wt%, and the average lithium collector coating amount on one side of the current collector of the positive electrode active material mixture layer (active material coating part) W2 is set The thickness of the positive electrode active material mixture layer (active material coating part) W2 was 120 g / in 2 (the thickness of the current collector was not included) was 109 μm, and the length of the positive electrode plate was 342 cm. In addition, in the negative electrode, MCBM is used as the negative electrode active material, and the thickness of the negative electrode active material mixture layer (active material coating portion) W4 (excluding the thickness of the current collector) δ is again 7 9 μπι 'length 354cm to make a battery. . (Example 1-16) As shown in Table 1, in Example 丨 _6, the lithium manganate powder of Example 1-1 was mixed with flaky graphite (relative to LiMn2O4) with an average particle diameter of 10 μm. Average particle size of flaky graphite of secondary particle size: 0.5 times), with acetylene carbon black (AB), and polyvinylidene fluoride, set the blending ratio to 83: 10: 2: 5 by weight%, and The positive electrode active material mixture layer (active material coating section) W2 has an average lithium manganate coating amount on one side of the current collector of 120 g / m2, and the positive electrode active material mixture layer (active material coating section) W2 has a paper size. Applicable to China National Standard (CNS) A4 specification (210 x 297 mm) -24- (Please read the notice on the back before filling this page) Order --------- · 522593 Intellectual Property of the Ministry of Economic Affairs Printed by the Consumer Cooperative of the Bureau A7 B7 V. Description of the invention (23). The thickness (excluding the thickness of the current collector) is set to 10 μm, and the length of the positive electrode plate is set to 3 4 2 cm. In the negative electrode, the negative electrode active material is made of amorphous carbon, and the thickness of the negative electrode active material mixture layer (active material coating portion) W4 (excluding the thickness of the current collector) is set to 79 μm, and the length is 3 54 cm. . (Examples 1-16-2 to 1-16-5) As shown in Table 1, in Examples 1 -1 6-2 to 1-1 6-5, Li / Mn except lithium manganate was removed. The ratios were set to 0.55, 0.58, 0.60, and 0.61, respectively, and the rest were produced in the same manner as in Examples 1 to 16. (Example 1-17) As shown in Table 1, in Examples 1-17, the acid powder of Example 1-1 was mixed with flaky graphite (relative to L i) having an average particle diameter of 10 μm. M n 2 〇 4 —average particle size of flaky graphite of secondary particle size: 0.5 times), and polyvinylidene fluoride, setting the blending ratio to 83: 12: 5 by weight%, and forming a positive electrode active material mixture layer ( Active material coating part) The average amount of lithium manganate coating on one side of the current collector was set to 120 g / m2. The thickness of the positive electrode active material mixture layer (active material coating part) W2 (excluding the current collector) Thickness) is set to 109 μm, and the length of the positive electrode plate is set to 342 cm. In the negative electrode, the negative electrode active material is made of amorphous carbon, and the thickness of the negative electrode active material mixture layer (active material coating part) W 4 (excluding the thickness of the current collector) is set to 7 9 μm and the length is 354 cm. battery. (Examples 1-17-2 to 1-17-5) As shown in Table 1, in Examples 1-17 · 2 to 1-17_5, the Li / Mn ratio of lithium manganate was set separately 0.55, 0.58, 0.60, this paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) ί Please read the note on the back first? Please fill in this page for more details.) Luo Zhuang -------- Order: -------- -25- Printed clothing for employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economy 522593 A7 B7_____ V. Description of the invention (24) Except for 0 · 6 1, the rest were made in the same manner as in Example 1 _ 丨 7. (Comparative Example 1 -1) As shown in Table 1, 'In Comparative Example 丨, except that the coating amount of lithium manganate was set to 75 g / m2, the thickness of the positive electrode active material mixture layer (active material coating portion) ( The thickness of the current collector is not included) is 150 μm, the length of the positive electrode plate is 276 cm, and the thickness of the negative electrode active material mixture layer (active material coating portion) (excluding the thickness of the current collector) is 109 μm ' The length of the negative electrode plate was set to 288 cm, and the rest were made in the same manner as in Example 1-1. (Comparative Example 1-2) As shown in Table 1, in Comparative Example 丨, except that the coating amount of lithium manganate was set to 165 g / m2, the thickness of the positive electrode active material mixture layer (active material coating portion) ( The thickness of the current collector is not included) is 150 μm, the length of the positive electrode plate is 276 cm, and the thickness of the negative electrode active material mixture layer (active material coating part) (excluding the thickness of the current collector) is 109 μm. The negative electrode plate is Except that the length was set to 288 cm, the rest were produced in the same manner as in Example 1-1. (Comparative Example 1-3) As shown in Table 1, in Comparative Examples 1-3, except that the acid bell powder was the same as that of Example 1-1, and flaky graphite (relative to LiMn2) having an average particle diameter of 18 μm 〇 average particle size of flaky graphite with secondary particle size: 〇9 times), and polyvinylidene fluoride, setting the blending ratio to 8 3: 7: 5 by weight, and a positive electrode active material mixture layer (active Material coating section) The average lithium manganate coating amount on one side of the current collector is set to 120g / m2, and the paper size of the positive electrode active material is applicable to China National Standard (CNS) A4 (210 X 297 mm). 26-(Please read the > i 咅 on the back? Matters before filling out this page) ▼ Install -------- Order ---------. 522593

V. Description of the invention (25) The thickness of the mouth J layer (active material coating part) (excluding the thickness of the current collector) is set to 1 03 μηι and the length of the positive electrode plate is set to μ9, and the negative electrode active material shell uses MCBM A battery was fabricated by setting the thickness of the negative electrode active material mixture layer (active material coating portion) (excluding the thickness of the current collector) to 80 μm and the length of 3 6 1 cm. (Comparative Examples 1 to 4) As shown in Table 1, in Comparative Examples 1 to 4, except that the lithium manganate powder of Example 1 to 1, and flaky graphite (relative to LiMn2O4) having an average particle diameter of 18 μm were used. Average particle diameter of flaky graphite of secondary particle size: 0.9 times), and polyvinylidene fluoride, setting the blending ratio to 7 8: 1 7: 5 by weight, and a positive electrode active material mixture layer (active Material coating section) The average lithium manganate coating amount on one side of the current collector was 120 g / rn2, and the thickness of the positive electrode active material mixture layer (active material coating section) was set (excluding the thickness of the current collector). It is set to 116 μm, and the length of the positive electrode plate is set to 334 cm. The negative electrode active material is MCBM, and the thickness of the negative electrode active material mixture layer (active material coating portion) (excluding the thickness of the current collector) is set to 80 μm. The length is 346cm, and a battery is made. < Test and Evaluation > Next, the following series of tests were performed on each battery in the examples and comparative examples prepared as described above. The batteries of the examples and comparative examples were charged and discharged, and the discharge capacity was measured. The charging condition is set to 4.2V constant voltage, limited current 5 A, 3 · 5 hours. The discharge conditions are set to 5 A constant current and termination voltage 2.7V 〇 This paper size applies Chinese National Standard (CNS) A4 (210 X 297 g t) (Please read the precautions on the back before filling this page) Γ iw · in flu n I «.—1 HI fe · * · I m 11 n in Yin Shen, Staff Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs-27- 522593 A7 _______B7 __ V. Description of the invention (26) In addition, measured according to the above conditions Charging battery output. The measurement conditions are 1A, 3 A, and 6A. Read the 5th-second voltage of each discharge current. The current value is plotted on the vertical axis with respect to the horizontal axis. Take an approximate straight line formed by three points and cross it with 2.7V. The product of the current value and 2 · 7ν is output. Moreover, the output (capacity) of each of the batteries of Examples and Comparative Examples was measured under 100% of the above conditions after repeated charging and discharging, and the maintenance ratio with respect to the initial output was expressed as a percentage ratio. Of course, the higher the maintenance rate, the better the life characteristics. These charging, discharging, and output measurements are performed in an environment with an ambient temperature of 25 ° C to 1 ° C. Then, the prepared battery was continuously charged at a constant current of 20a at normal temperature, and the behavior of the battery was observed. The results are shown in Table 2 below. Phenomenon is caused by the release of the gas composed of the volatiles of the electrolyte after the cracking valve is cracked. To compare the extent of this gas release, the surface temperature of the battery immediately after the phenomenon occurred was measured. Furthermore, after the gas was released, it was confirmed whether the battery container was changed >. In “Table 2”, “〇” means that no deformation of the battery container was recognized at all; “△” means that the deformation of several battery containers was recognized; and “χ” means that the major deformation of the battery container was recognized. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) f Please read the details on the back before filling this page) -------- Order -------- -· Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economy -28-522593 A7 B7 V. Description of Invention (27)

Table 2 Capacity (Ah) Initial output safety (W) Maintenance rate (%) Battery surface temperature (° C) Battery appearance Example 1-1 5.38 770 90 220 Δ Example 1-2 6.36 750 90 180 ϋ Example 1 -2-2 6.36 750 93 180 ◦ Example 1-2 -3 6.24 750 94 180 ◦ Implementation W 1-2-4 5.24 750 95 180 0 Example 1-2-5 5.76 750 95 180 ◦ Example 1-3 6. 99 710 90 150 ϋ Example 1-4 6.47 715 88 170 〇 Example 1-5 6.25 730 92 190 ϋ Implementation 彳 1) 1-6 6.36 760 90 180 ϋ Example 7 6.36 780 90 210 Δ Implementation You j 1-8 6.36 780 9 0 190 0 implementation Θ 1-9 6.36 770 90 180 0 embodiment 1-10 6.36 770 90 170 ϋ embodiment 1-11 6.36 800 91 180 实施 implementation life j 1 -12 6.36 800 94 180 ◦ Example 1-13 6.24 800 95 180 ◦ Example 1-14 6.24 800 96 180 0 Implement your j 1 -1 5 5.76 800 96 180 0 Implement your j 1-1 6 5. 94 820 91 120 ϋ Example 1-1 6-2 5. 94 820 94 120 ϋ Example 1-16-3 5.82 820 95 120 ◦ Implementation order j 1-1 6-4 5.82 820 96 120 ϋ Example 1-1 6- 5 5.37 820 96 120 ϋf Example 1-17 5. 94 790 91 1 20 0 Example 1-17-2 • 5. 9 4 790 94 120 ϋ Example 17 -3 5. 82 790 95 120 ϋ Example 1-1 7-4 5.82 790 96 120 ϋ Example 1-1 7 -5 5 .37 790 96 120 ϋ more like 丨) 1-1 5 .23 790 90 330 X compare j 1-2 7.06 630 90 150 0 compare life j 1-3 6.49 645 84 150 ϋ compare you j 1- 4 6.21 740 92 310 X ---------- IM -------- Order --------- (Please read the back of tf first; please fill in this page before paying attention ) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs as shown in Table 2. Among the batteries of Examples 1-1 to 1-5, high-capacity, high-output batteries can be obtained, and the batteries are continuously charged. The behavior was also stable. The maximum battery surface temperature at this time is 150 ° C ~ 220 ° C. In Comparative Example 1 -1 where the coating amount of lithium manganate is less than 80 g / cm2, although a high-capacity and high-output battery can be obtained, the Chinese national standard (CNS) A4 specification (210 X 297 mm) -29- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 522593 A7 ---------- ----- B7_ V. Description of the invention (28) The battery behavior during continuous charging will be As the battery shape becomes fierce, the surface temperature of the battery exceeds 30 ° C. On the other hand, among the batteries of Comparative Example 1-2 which are higher than 160 g / cm2, the battery behavior during continuous charging is stable, but as the output decreases, the result will be unsuitable for use in electric vehicle batteries. Similarly, in the battery of Comparative Example 3, the positive electrode conductive material: the amount of graphite is less than 8% by weight, and as a result, the output is reduced. On the other hand, in the comparative example W battery in which the amount of graphite in the positive electrode conductive material is higher than 16% by weight, a high-capacity and high-output battery can be obtained. The battery surface temperature exceeds 31 ° C. % In the batteries of Examples 1 to 6 of Example 1-6 to Example 5 in which graphite is mixed with amorphous carbon in the conductive material of the positive electrode, a battery with a higher output can be obtained. In the battery of Example 丨 _6 to Example 1-10 where the amorphous carbon uses graphitized carbon black, the particle size ratio of graphite of the conductive material is 0 · 2 to the secondary particle diameter of the lithium manganate of the positive electrode active material. 〇8 的 实施 例 8 ～ 实施 例 1-10, can obtain higher output. With respect to the secondary particle diameter of lithium manganate, and the ratio of the particle size ratio of the conductive material graphite to less than 0.2, the battery surface temperature during continuous charging was 2 ° C, which was slightly higher than that of Example 1- A small battery of 8 to 1 -1 〇. In the examples of non-shaped carbon using acetylene carbon black, the examples 1-16-5 batteries, higher output can be obtained, and the output retention rate after 100 charge and discharge is also high. Examples of lithium manganate having a Li / Mn ratio of 0.55 or more ι_12 ~ Example 1-14, Example 1-2-2 ~ Example U-4, Example 1-16-2 ~ Applicable to this paper size China National Standard (CNS) A4 Specification (210 X 297 male f) · Install -------- Order --------- f Please read the unintentional matter on the back before filling in this page}- 30- 522593

AT B7 V. Description of the Invention (29) The batteries of Examples 1-16-4, Examples 2-17-2 to 7-4 have extremely high output retention, but the Li / Mn ratio of lithium manganate is high The batteries of Example 1-15, Example 1-2-5, Example ι_16-5, and Example 1 -1 7-5 above 0.60 will result in lower capacity, so we know The Li / Mn ratio is preferably in the range of 0.5 to 0.60. Example 1-16, Example 1-16-2 to Example ΐ-16 · 5, Example bu using negative carbon for the negative plate Example 17-2 ~ Adding only the battery of Example 1-17-5 ', it can be learned that the output is extremely high, and the output maintenance rate is very high. Therefore, the batteries of Examples 1-16, 1-16-2 to 1-16-5, 1-17, and 1.17-2 to Bu 17-5 can be said to have high capacity, high output, and good safety. Overall balanced battery. As described above, the cylindrical lithium-ion battery 20 according to this embodiment is a battery that behaves extremely smoothly and has excellent safety when the battery is in an abnormal state. This two-capacity, high-output, and extremely safe battery is especially suitable for HEV power supplies. (Second implementation Xiong Yan 1 The following description of the second embodiment of the use of the non-aqueous electrolyte secondary battery of the present invention in an EV «cylindrical lithium-ion battery will be described with reference to the drawings. As shown in Fig. 2, the ferrous acid of the positive electrode active material is subjected to (LiMn2〇4)

Hou Cheng Sheng A of powder and conductive materials, and this special enemy, adhesive polyvinylidene fluoride (PVDF), according to the specific mix of "Kunhe", and add the paper scale thorn caps and other miscellaneous materials (please First read the Italian matter on the back of the book in secret. Fill out this f > ▼ Load -------- Order --------- ^ M_w— -31- 522593 A7 V. Description of the Invention (30) Solvent N-methyl-2-pyrrolidone (NMp), kneaded with krypton to form a mouthpiece. This material was then coated on both sides of a 20 μm-thick Shaoxing (positive electrode body). At this time on the positive plate An uncoated portion with a width of 50 mm remains on one edge in the length direction. After drying, stamping, and cutting, a strip-shaped positive plate having a width of 330 mm, a specific length described later, and a specific thickness at the application site of the active material mixture is obtained. The bulk density of the positive electrode active material mixture layer was set to 2.65 g / cm3. A gap was provided in the portion where the slurry was not coated on the positive electrode plate, and the remaining portion without the gap was used as a conductive sheet. In addition, adjacent conductive layers were used. Sheets are set at 50mm intervals, and the width of the conductive sheet is set to 10mm. (Negative electrode) Can be stored or stored after charging and discharging. Out of 92 parts by mass of lithium specific carbon powder, 8 parts by mass of polyvinylidene fluoride added with an adhesive, and N-methyl-2-pyrrolidine, which is a dispersant, was added thereto, and a slurry was formed after kneading. This slurry was applied to both sides of a rolled copper foil (negative electrode current collector) with a thickness of 10 μίη. At this time, an uncoated portion with a width of 50 mm remained on one side edge of the negative electrode plate in the longitudinal direction. After drying, stamping, and cutting, a strip-shaped negative plate having a width of 305 mm, a specific length described later, and a specific thickness of the active material coating portion is obtained. The negative plate is compressed to have a void ratio of the negative active material mixture layer of about 35%. On the negative plate At the uncoated part, a notch is set in the same way, and the remaining part without the notch is used as a conductive sheet. Set the adjacent conductive sheet at a 50mm interval, and set the width of the conductive sheet to 10mm 〇 (production of the battery) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the >!. On the back before filling in this page) —Order · -------- Ministry of Economic Affairs Printed by the Intellectual Property Bureau's Consumer Cooperatives -32-522593 Ministry of Economic Affairs Printed by the Consumer Bureau of the Production Bureau A7 B7 V. Description of the invention (31) The strip-shaped positive plate and the negative plate obtained above are in a way that does not directly contact the two electrode plates, with a width of 31 mm and a thickness of 40 μm. The polyethylene separator is wound. At this time, the conductive sheets 1 0 9 of the positive electrode plate and the negative electrode plate are respectively located at the end positions of the winding group opposite to the two sides. In addition, the positive electrode plate, the negative electrode plate, and the separator are adjusted. The length of the plate was set to 65 to 01 mm in the diameter of the winding group 106. The conductive sheet 1 09 derived from the positive electrode plate was deformed and all of it were brought into contact with the poles extending from the line almost on the winding core π 1 of the winding group 106. Around the pillar (positive external terminal 10), the wall surface of the flange 107 which protrudes integrally, and then the conductive sheet 109 and the wall surface of the flange 107 are welded and fixed by ultrasound. In addition, the connection operation of the negative external terminal i i ′ and the conductive sheet 109 led from the negative plate is also performed in the same manner as the connection operation of the positive external terminal 101 and the conductive sheet 109 derived from the positive plate. Then, an insulating coating 108 is applied over the entire periphery of the flange 107 of the positive external terminal 101 and the negative external terminal 101 ·. In this insulating coating, the 'base material is made of polyimide' and an adhesive tape coated with an adhesive made of hexamethylacrylate on one side is used. This adhesive tape was wound from the wall surface of the flange 107 to the outer wall of the winding group 106 in a few layers to form an insulation coating 108. Adjust the number of windings so that the maximum diameter portion of the winding group 106 is the insulation coating 108. The maximum diameter is only slightly smaller than the inner diameter of the stainless steel battery container 105, and the winding group 106 is inserted into the battery. Inside the container 105. The battery container 105 has an outer diameter of 67mm and an inner diameter of 66mmo. Then, it will abut against the alumina disc-shaped battery cover 104. The back part of the paper is sized to the Chinese National Standard (CNS) A4 (210 X 297 mm). ) (Please read the notes on the back before filling this page)

-33- 522593

V. Description of the invention (32) The second ceramic washer with thickness of 2mm, inner diameter of 16mm and outer diameter of 25mm printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is embedded in the front end to form a positive external terminal The pole and the front end constitute the pole of the negative external terminal 101. In addition, a first ceramic gasket 103 with a thickness of 2 mm, an inner diameter of 16 mm, and an outer diameter of 28 mm on the back portion of the disc-shaped battery cover 104 made of alumina was placed on the battery cover 104, and the positive electrode external terminal 101 and the negative electrode The external terminals 101 pass through the first ceramic washer 103 respectively. Then, the peripheral surface of the battery cover 104 is fitted into the opening of the battery container 105, and the entire area of the contact portion between them is welded by laser. At this time, the positive external terminal 101 and the negative external terminal 101 are holes formed through the center of the battery cover 104 and protrude outside the battery cover 104. Then, the first ceramic washer 103 and the metal washer i i 4 which is smoother than the bottom surface of the metal cap body 102 are sequentially moved into the positive external terminal 101 and the negative external terminal 10 respectively. In addition, the battery cover 104 is provided with a cleavage valve 110 that reduces the internal pressure of the battery in response to an increase in the internal pressure of the battery. The cracking pressure of the cracking valve 11 〇 is set to 1.3 × 106 to 1.8 × 106 Pa. Next, 'the cap body 102 is screwed to the positive external terminal 1 〇1, the negative external terminal 10 Γ, respectively, through the second ceramic washer 103,' the first ceramic washer 103 and the metal washer 114, the battery cover 1 〇4 is locked between the flange 107 and the cap body 102. The closing torque value is about 7 N · m. In addition, the metal ring 114 does not rotate until the end of the lock industry. In this state, the compression of a 0-ring 116 made of rubber (EPDM) between the back of the battery cover 104 and the flange 107 is used to compress the power generating element inside the battery container 105 from outside air. Stop it. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 'Order --------- (Please read the precautions on the back before filling this page) 522593 Intellectual Property Bureau, Ministry of Economic Affairs A7 B7 printed by the employee's consumer cooperative V. Description of the invention (33) Then the non-aqueous electrolyte is poured into the battery container of a certain amount from the filling port 1 1 5 provided on the battery cover 104, The filling port 115 is sealed to complete the cylindrical bell ion battery 120. In a non-aqueous electrolyte, hexafluorinated acid H (LiPF6) is dissolved in a mixed solution of ethyl ether carbonate, dimethyl carbonate, and diethyl carbonate in a volume ratio of 1: 1: 1. Mohr / Liter. In addition, the cylindrical via ion battery 120 is not provided with a current blocking mechanism such as a PTC (Positive Temperature Coefficient) element that blocks or reduces current as the temperature of the battery container 105 rises. Next, an embodiment of a cylindrical bell ion battery 120 according to this embodiment will be described. A battery of a comparative example produced for comparison is also described. (Example 2-1) As shown in Table 3 below, in Example 2_ 丨, the primary particle diameter of the positive electrode active material was about 1 to 2 μm, the secondary particle diameter was about 20 μm, and the atomic ratio of Li to Mη (Li / Mn ratio) 0.52 lithium manganate (LiMn204) powder, and flaky graphite with an average particle diameter of 18 μm, and polyvinylidene fluoride, and the blending ratio β is 9%. 5: 5, and The positive electrode active material mixture layer (active material coating portion) has an average lithium manganate coating amount on one side of the current collector of 270 g / m2 '. The positive electrode active material mixture layer (the thickness of the active material coating portion (not including The thickness of the current collector) was set to 226 μm, and the length of the positive electrode plate was set to 615 cm. The average particle diameter of the flaky graphite was 0.9 times the secondary particle diameter of LiMn204. In addition, in the negative electrode plate, the negative electrode active material MCBM with mesophase spherical graphite is used, and the negative electrode (please refer to Mtf first; please fill in the cover sheet) * II — IIII. III I ----- This paper size applies Chinese national standards (CNS) A4 specification (21〇297 g) 522593 A7 _B7___ 5. Description of the invention (34) Active substance mixture The thickness of the active material coating part (excluding the thickness of the current collector) is set to 150 μm and the length is 663 cm. In addition, the average particle size of flaky graphite can be adjusted by screening. ---------- ^ IM -------- Order · -------- (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Applicable to China National Standard (CNS) A4 specification (210 X 297g t) 522593 Λ7B7 V. Description of invention (35

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522593 V. Description of the invention (36) In addition, when the electrode plate is wound, the positive electrode plate does not protrude from the negative electrode plate in the winding direction according to the innermost winding of the winding, and even at the outermost In the way that the positive plate does not protrude from the negative plate in the winding direction, the length of the negative plate is set to be 18 cm longer than the length of the positive plate. In addition, even in the winding direction and the vertical direction, the width of the negative electrode active material coated portion is larger than that of the positive electrode active material coated portion such that the positive electrode active material coated portion does not protrude from the negative active material coated portion. The width exceeds 5 mm (the same applies to the following examples and comparative examples). (Example 2-2) As shown in Table 3, in Example 2-2, the thickness of the positive electrode active material mixture (active material coating portion) was set in addition to setting the coating amount of lithium manganate to 300 g / m2 '. (The thickness of the current collector is not included) is set to 252 μm, the length of the positive electrode plate is set to 565 cm, the thickness of the negative electrode active material mixture (active material coating portion) (excluding the thickness of the current collector) is set to 166 μm, and the length of the negative plate is set to 5 Except for 83 cm, the rest were made as in Example 2-1. (Examples 2-2-2 to 2, 2-5) As shown in Table 3, in Examples 2-2-2 to 2-2-5, except for the Li / Mn ratio of lithium manganate, Except that they were set to 0.55, 0.58, 0.60, and 0.61, the rest were made as in Example 2-2. (Example 2-3) As shown in Table 3, in Examples 2 to 3, in addition to setting the coating amount of lithium manganate to 3 3 Og / m2, the positive electrode active material mixture (active material coating portion) The thickness (excluding the thickness of the current collector) is set to 277μιη, the length of the positive electrode plate is set to 5 2 3 cm, and the thickness of the negative electrode active material mixture (active material coating portion) is thick. This paper applies the Chinese National Standard (CNS) A4 specification (210 X 297g t) • I _ I _ — II I, Tellurium t (Please read the precautions on the back before filling out this page) Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -38- 522593 A7 B7 Consumption of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the cooperative V. Description of the invention (37 degrees (excluding the thickness of the current collector) is set to 183 μm, and the length of the negative plate is set to 541 cm. The rest are the same as in Example 2). (Example 2-4) Such as As shown in Table 3, in Example 2-4, the fibrous acid powder as in Example 2-1 and flaky graphite having an average particle diameter of 18 μm (relative to the flaky graphite having a secondary particle diameter of LiMn204) (Average particle size: 〇9 times), and PVDF 'will set the blending ratio The weight percentage was set to 90: 3: 7, and the average amount of lithium manganate coating on one side of the current collector of the positive electrode active material mixture layer (active material coating portion) was set to 300 g / m2. The thickness of the mixture layer (active material coating portion) (excluding the thickness of the current collector) was set to 252 μm ′ and the length of the positive electrode plate was set to 565 cm. In addition, in the negative electrode, MCBM was used as the negative electrode active material, and the negative electrode active material mixture was used. The thickness of the layer (active material coating part) w 4 (excluding the thickness of the current collector) was set to 166 μm, and the length was 5 83 cm to produce a battery. (Example 2-5) As shown in Table 3, in Example 2-5 , Like the lithium manganate powder of Example 2.i, flaky graphite with an average particle diameter of 8 μm (average flaky graphite with secondary particle diameter of LiMhO4: 0.9 times), and polyvinylidene fluoride , Setting the blending ratio to be 9 wt%: 7: 3, and setting the average amount of acidic acid bell coating on one side of the current collector of the positive electrode active material mixture layer (active material coating portion) to 300 g / m2, The thickness of the positive electrode active material mixture layer (active material coating portion) ( The thickness of the current collector is not included) is set to 260 μm, and the length of the positive electrode plate is set to 5 56 cm. In addition, in the negative electrode, MCBM is used as the negative electrode active material, and the negative electrode active material mixture is used as a mixture. 3 9 — ------- -^ — M · 装 -------- Order --------- (Please write the page of Mtf with the intention of δ, and then write this page> 522593 A7 B7___ 5. Description of the invention ( 38) The thickness of the layer (active material coating portion) W4 (excluding the thickness of the current collector) was set to 166 μm and the length was 574 cm to prepare a battery. (Example 2-6) As shown in Table 3, in Example 2-6, the acid bell powder as in Example 2-1 was mixed with flaky graphite (relative to LiMn204 Average particle size of flaky graphite of secondary particle size: 〇9 times), graphitized carbon black (KB), and polyvinylidene fluoride, and set the blending ratio to 90: 4: 1: 5 by weight, and The average amount of lithium manganate coating on one side of the current collector of the positive electrode active material mixture layer (active material coating portion) was set to 300 g / m2, and the thickness of the positive electrode active material mixture layer (active material coating portion) was ( The thickness of the current collector is not included) is set to 252 μm, and the length of the positive electrode plate is set to 565 cm. In the negative electrode, a MCBM 'was used as the negative electrode active material, and the thickness of the negative electrode active material mixture layer (active material coating part) (excluding the thickness of the current collector) was set to 166 μm and the length was 583 cm to produce a battery. (Example 2-7) As shown in Table 3, in Example 2-7, the fibrous acid powder as in Example 2_i and flaky graphite (relative to LiMn2O4) with an average particle diameter of 2 μm were used. Average particle size of flaky graphite of secondary particle size: 〇; [times], and graphitized isthmus black (KB) 'and polyvinylidene dichloride, and the blending ratio is set to 90% by weight: 4: 1: 5. Set the average amount of lithium manganate coating on one side of the current collector of the positive electrode active material mixture layer (active material coating section) to 300 g / m2. The thickness (excluding the thickness of the current collector) is set to 252 μηι, and the long-term production of the positive plate is based on the Chinese National Standard (CNS) A4 specification (210 X 297 mm). 401—Γ Read the i on the back first Transcript: > Fill in this I again > --- ^ --------- Printed by the Consumers' Cooperative of Intellectual Property Bureau of the Ministry of Economy 522593 A7

Set to 565cm. In addition, in the negative electrode, the MCBM is used as the negative electrode active material, and the thickness of the negative electrode active material mixture layer (active material coating part) (excluding the thickness of the current collector) is set to 166 μm, and the length is 5 8 3 cm, $ to make a battery. (Example 2-8) As shown in Table 3, in Example 2.8, the lithium manganate powder of Example 2 was mixed with flaky graphite (relative to LiMri204 secondary particle diameter) with an average particle diameter of 4 μm. Average particle size of flaky graphite: 〇2 times), with graphitized carbon black (KB), and polyvinylidene fluoride, set the blending ratio to 90: 4: 1: 5 by weight, and set the positive active material The mixture layer (active material coating section) has an average current coating amount of the acidic acid bell on one side of the current collector set to 300 g / m2. The thickness of the positive electrode active material mixture layer (active material coating section) (excluding the current collector) Thickness) was set to 252 μηι, and the length of the positive electrode plate was set to 565 cm. In the negative electrode, a battery was fabricated by using MCBM 'as the negative electrode active material and setting the thickness of the negative electrode active material mixture layer (active material coating portion) (excluding the thickness of the current collector) to 166 μm and 583 cm in length. (Example 2-9) As shown in Table 3, in Example 2-9, the lithium manganate powder as in Example 2-1 was mixed with flaky graphite having an average particle diameter of 18 μm (secondarily to LiMn204 Average particle size of flaky graphite: 0.5 times), with graphitized carbon black (KB) 'and polyvinylidene fluoride, set the blending ratio to 90: 4: 1: 5 by weight, and The average amount of lithium manganate coating on one side of the current collector of the positive electrode active material mixture layer (active material coating part) is set to this paper standard. Applicable to China National Standard (CNS) A4 (210 X 297 g) (please first (Please read the notes on the back and fill in this page) ▼ Install -------- Order --------- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-4 Printed by the cooperative 522593 V. Description of the invention (40) 3 00 g / m, set the thickness of the positive electrode active material mixture layer (active material coating part) (excluding the thickness of the current collector) to 252 μπι, and set the length to 5 65 cm. In the negative electrode, MCBM was used as the negative electrode active material, and the thickness of the negative electrode active material mixture layer (active material coating part) (excluding the thickness of the current collector) was set to 166 μm and the length was 5 83 cm to produce a battery. (Example 2-10) As shown in Table 3, in Example 2 "〇, lithium manganate powder 'as in Example 2-1 and flaky graphite (relative to LiMhO4 secondary particles) having an average particle diameter of ihm were used. Average diameter of flaky graphite: 0.8 times), with graphitized carbon black (KB), and polyvinylidene fluoride, the blending ratio is set to 90% by weight: 0: 4: 1: 5, and the positive electrode is The average coating amount of lithium manganate on one side of the current collector of the active material mixture layer (active material coating portion) is set to 300 g / m '. The thickness of the positive electrode active material mixture layer (active material coating portion) is ( The thickness of the current collector is not included) is set to 2 52 μηι, and the length is set to 5 65 cm. In addition, in the negative electrode, the active material of the negative electrode is% c Β Μ, and the negative electrode active material mixture layer (active material coating The thickness (excluding the thickness of the current collector) was set to 1 66 μm, and the length was 583 cm, to make a battery. (Example 2-Π) As shown in Table 3, in Example 2-11, it will be implemented as The lithium manganate powder of Example 2-1 and the flaky graphite (relative to the secondary particle size of LiMn204 Average graphite particle size: 05 times), with acetylene carbon black (AB), and polyvinylidene fluoride, the blending ratio is set to the weight of this paper. The paper size applies the Chinese National Standard (CNS) A4 specification (210 x 297 meals) ) I 42 — f Please read the notes on the back of tf before filling out this page) ▼ Install ------- --Order --------- 522593

V. Description of the invention (41) The printed amount% of the employee cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is 90: 4: 1: 5, and the average current collector single side of the positive electrode active material mixture layer (active material coating ° 卩) The coating amount of the acidic bell was set to 300 g / m2, the thickness of the positive electrode active material mixture layer (active material coating portion) (excluding the thickness of the current collector) was set to 252 μm, and the length of the positive electrode plate was set to 565cm. In addition, in the negative electrode, MCBM was used as the negative electrode active material, and the thickness of the negative electrode active material mixture layer (active material coating part) (excluding the thickness of the current collector) was set to 166 μm and the length was 583 cm to prepare a battery. (Example 2-12) As shown in Table 3, in Example 2 the primary particle diameter of the positive electrode active material was about 1 to 2 μm, the secondary particle diameter was about 20 μm, and the atomic ratio of Li to Mn (Li / Mn ratio) 0.55 lithium manganate (LiMn204) powder, flaky graphite with an average particle size of 10 μm (average flaky graphite with secondary particle size of LiMri2 0: 0.5 times), and acetylene carbon black (AB), and polyvinylidene fluoride, set the blending ratio to 90: 4: 1: 5 by weight%, and make the average current collector of the positive electrode active material mixture layer (active material coating part) The amount of acid bell coating was 300 g / m2, the thickness of the positive electrode active material mixture layer (active material coating part) (excluding the thickness of the current collector) was set to 252 μm ′, and the length was set to 565 cm. In the negative electrode, MCBM was used as the negative electrode active material, and the thickness of the negative electrode active material mixture layer (active material coating portion) (excluding the thickness of the current collector) was set to 166 μm and the length was 5 83 cm to prepare a battery. (Example 2-13) As shown in Table 3, in Example 2-13, the positive electrode active paper was again applied to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ---- ---------------- Order --------- (Please read the notice on the back before filling out this page) -43 — 522593 Employees of Intellectual Property Bureau, Ministry of Economic Affairs Printed by the Consumer Cooperative A7 ____B7____ 5. Description of the invention (42) Lithium manganate (LiMn2) with a primary particle size of about 1 to 2 μm, a secondary particle size of about 20pm, and a Li to Mn atomic ratio (Li / Mn ratio) of 0.58. 4) Powder, flaky graphite with an average particle size of 10 μm (average flaky graphite with a secondary particle size of LiMn204: 0.5 times), with acetylene carbon black (AB), and polyvinylidene chloride ' The blending ratio was set to 90: 4.1.5 by weight%, and the average coating amount of the acidic acid bell on one side of the current collector of the positive electrode active material mixture layer (active material coating portion) was set to 300 g / m2. The thickness of the active material mixture layer (active material coating portion) (excluding the thickness of the current collector) was set to 252 μm, and the length was set to 565 cm. In the negative electrode, MCBM was used as the negative electrode active material, and the thickness of the negative electrode active material mixture layer (active material coating part) (excluding the thickness of the current collector) was set to 166 μm and the length was 583 cm to prepare a battery. (Example 2-14) As shown in Table 3, in Example 2-14, the primary particle diameter of the positive electrode active material was about 1 to 2 μm, the secondary particle diameter was about 20 μm, and the atomic ratio of Li to Mn (Li / Mn ratio) 0.60 lithium manganate (LiMn2O4) powder, flaky graphite with an average particle size of 10 μm (average flaky graphite with secondary particle size of LiMn2O4: 0.5 times), and acetylene Carbon black (AB) and polyvinylidene fluoride, the blending ratio is set to 9% by weight: 0: 4: 1: 5, and the average current collector sheet of the positive electrode active material mixture layer (active material coating portion) is set. The coating amount of lithium manganate on the surface was set to 300 g / m2, the thickness of the positive electrode active material mixture layer (active material coating portion) (excluding the thickness of the current collector) was set to 252 μm, and the length was set to 565 cm. . In addition, in the negative electrode, the negative electrode active material uses MCBM, and the negative electrode active material mixture layer is applied to the Chinese national standard (CNS) A4 specification (210 X 297 meals). 44- (Please read the precautions on the back first. (Fill in this page) nnn ian n in m ^ ^ 4 im βϋ IV i in nnf · 522593 A7 B7 V. Description of the invention (43 (active shell coating section) The thickness (excluding the thickness of the current collector) is set to 166 μιη, A battery was fabricated with a length of 583 cm. (Example 2-15) As shown in Table 3, in Examples 2 to 15, the primary particle diameter of the positive electrode active material was about 1 to 2 μπχ, and the secondary particle diameter was about 2 μ. μm, lithium manganate (LiMn204) powder with Li to Mn atomic ratio (Li / Mn ratio) of 0.6i, and flaky graphite with an average particle size of 10 μm (relative to LiMn204: flaky graphite with a secondary particle size) (Average particle size: 05 times), with acetylene carbon black (AB), and polyvinylidene fluoride ', the blending ratio is set to a weight G /. Of 9 0: 4: 1: 5, ϋ the positive electrode active material mixture layer (Active material coating section) The average coating amount of manganic acid on one side of the current collector was set to 300 g / m2, and The thickness of the active material mixture layer (active material coating part) (excluding the thickness of the current collector) was set to 252 μm, and the length was set to 565 cm. In addition, in the negative electrode, MCBM was used as the negative electrode active material, and the negative electrode active material mixture was used. The thickness of the layer (active material coating portion) (excluding the thickness of the current collector) was set to 166 μm and the length was 5 83 cm to produce a battery. (Example 2-16) As shown in Table 3, in Example 2- 丨In 6, the fibrous acid bell powder as in Example 2-1 and flaky graphite with an average particle size of 10 μm (average flaky graphite with a secondary particle size of LiMn204: 0.05 times), and Acetylene carbon black (AB) and polyvinylidene fluoride, the blending ratio is set to 90: 4: 1: 5 by weight%, and the average current collector sheet of the positive electrode active material mixture layer (active material coating part) is set. The coating amount of lithium manganate on the surface is set to 3 00g / m2, and the positive electrode active material mixture layer (active material coating part) is closed (please close the jade on the back, and then fill out the wooden page) ▼ pack --- ----- tr --------- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-45- Printed by the Consumer Bureau of the Production Bureau 522593 A7 V. Description of the invention (44) The thickness (excluding the thickness of the current collector) is set to 252 μm and the length is set to 605 cm. In addition, in the negative electrode, the negative electrode active material is amorphous Carbon ', and the thickness of the negative electrode active material mixture layer (active material coating part) (excluding the thickness of the current collector) was set to 133 μm and the length was 62 3 Cm to produce a battery. (Examples 2-16-2 to 2-16-5) As shown in Table 3, in Examples 2-16-2 to 2-16-5, except for the Li / Mn ratio of lithium manganate, Except for the settings of 0.55, 0.58, 0.60, and 0.61, the rest were made as in Example 2-16. (Example 2-17) As shown in Table 3, in Example 2-17, the manganate bell powder as in Example 2-1 was mixed with flaky graphite (relative to LiMn2O) having an average particle diameter of 10 μm. 4 average particle size of flaky graphite with secondary particle size: 0.5 times), and? κ Partially messy ethylene 'Set the blending ratio to 9 wt%: 5 · 5, and set the average amount of lithium manganate coating on one side of the positive electrode active material mixture layer (active material coating part) The thickness (excluding the thickness of the current collector) of the positive electrode active material mixture layer (active material coating portion) was 300 g / m2, and the length was 605 cm. In the negative electrode, an amorphous carbon was used as the negative electrode active material, and the thickness of the negative electrode active material mixture layer (active material coating portion) (excluding the thickness of the current collector) was set to 133 μm and the length was 623 cm to prepare a battery. (Examples 2-17-2 to 2-17-5) As shown in Table 3, in Examples 2-17-2 to 7-5, the Li / Mn ratio 'except for the hardening acid was set separately. 0.55, 〇58, 0 60, This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -4 6- ^ -------- Order -------- -f Please read the main items on the back before filling in this page) 522593 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description (except 45 0 · 61, the rest are made as in Example 2-17) (Comparative Example 2-1) As shown in Table 3, in Comparative Example 丨, in addition to coating lithium manganate ϊ δ to 260 g / m ', the positive electrode active material mixture layer (active material The thickness of the coating part (excluding the thickness of the current collector) is set to 218 μηι, and the length a is set to 6 3 3 cm ', and the thickness of the negative electrode active material mixture layer (active material coating part) is not included. The thickness of the current collector) was set to 144 pm, and the length of the negative electrode plate was set to 6 5 1 cm. The rest were made as in Example 2 -1. (Comparative Example 2-2) As shown in Table 3, in Comparative Example 2 -2, in addition to coating lithium manganate 3 4 0 g / m2 'Set the thickness of the positive electrode active material mixture layer (active material coating part) (excluding the thickness of the current collector) to 285 μm, and the length to 5 11 cm, and the negative electrode active material mixture The thickness of the layer (active material coating part) (excluding the thickness of the current collector) was set to 189 # ^, and the length of the negative electrode plate was set to 5 2 9 cm, and the rest were made in the same manner as in Example 2 -1. (Comparative Example) 2-3) As shown in Table 3, in Comparative Example 2_3, except that the lithium manganate powder of Example 2-1 was mixed with flaky graphite (relative to the secondary particle diameter of LiMr ^ O4) having an average particle diameter of 8 μm. Flaky graphite average particle size: 0.9 times), and polyvinylidene fluoride, setting the blending ratio to 9: 2: 7 by weight%, and setting the positive electrode active material mixture layer (active material coating portion) The average coating amount of lithium manganate on one side of the current collector is set to 300g / m2, and the positive electrode active material < Please read the back of the page before; i. · --------. 522593 A7 B7 V. Description of the invention (46) The thickness of the mixture layer (active material coating part) (excluding the thickness of the current collector) Degree) is set to 249μΓη, and the length is set to 568cm ', and the negative electrode active material is MCBM, and the thickness of the negative electrode active material mixture layer (active material coating portion) (excluding the thickness of the current collector) is set to 166μιη' length 5 8 6 cm while making the battery. (Comparative Example 2-4) As shown in Table 3, in Comparative Example 2_4, except that the lithium manganate powder of Example 2-1 was mixed with flaky graphite (relative to LiMn2 04 Average particle size of flaky graphite: 009 times), and polyvinylidene fluoride, the blending ratio is set to a weight Q / ❶ of 8 6: 8: 6, and a positive electrode active material mixture layer (active material coating Cloth part) The average amount of coated acid on one side of the current collector is set to 300 g / m2, and the thickness of the positive electrode active material mixture layer (active material coating layer) (excluding the thickness of the current collector) is set to 2 6 3 μm 'and set the length to 5 5 3 cm, while the negative electrode active material uses MCB Μ, and the thickness of the negative electrode active material mixture layer (active material coating part) (excluding the thickness of the current collector) is set to 160 μm, length 5 7 1 cm, to make a battery. < Test and Evaluation > Next, the following series of tests were performed on each battery in the examples and comparative examples prepared as described above. The batteries of the examples and comparative examples were charged and discharged, and the discharge capacity was measured. The charging conditions are set to 4 · 2 V constant voltage, limited current 80A, 3.5 hours. The discharge conditions are set to a constant current of 20A and a termination voltage of 2.7V. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) (please fill in this page with the items on the back of Mtt) -n an n · fn «II ^ in flu If .1— Economy Printed by the Ministry of Intellectual Property Bureau's Consumer Cooperatives-48 — 522593 A7 B7 V. Description of the Invention (47 Printed by the Ministry of Economic Affairs 'Intellectual Property Bureau's Consumer Cooperatives. In addition,' Measure the battery discharge output in the state of charge according to the above conditions. The test conditions are 20A, 40A, 80A, read the 5th-second voltage of each discharge current, draw the point on the vertical axis with respect to the current value on the horizontal axis, take an approximate straight line formed by three points, and cross the current value at the intersection with 2 · 7ν. The product of 2 · 7ν is output. Furthermore, the batteries of the examples and comparative examples were charged and discharged repeatedly under the above conditions, and then the output (capacity) was measured. The retention rate is expressed as a percentage rate. Of course, if the maintenance rate is in Vietnam, the life characteristics will be better. These charging, discharging, and output measurements will be performed at an ambient temperature of 2 5 ± 1 ° C regardless of which. Then, Will make the electricity The battery was continuously charged at a constant current of 808 at normal temperature, and the behavior of the battery was observed. The results are shown in Table 4. The phenomenon is that after the cracking valve is cracked, the gas composed of the volatiles of the electrolyte is released. In order to compare the degree of this gas release, the surface temperature of the battery immediately after the phenomenon occurred was measured. Furthermore, after the gas was released, it was confirmed whether the battery container was branched. In addition, in Table 2, "〇" means that no battery container was confirmed at all. "△" means to recognize the deformation of several battery containers; "X" means to recognize the large deformation of the battery container. (Please read the notice on the back before filling this page) ▼ 装 ·- ----- Order · -------- -49- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 522593 V. Description of Invention (48 Table 4

As shown in Table 4, among the batteries of Examples 2 to 5 of Example 2, a high-capacity, high-output battery can be obtained, and the battery behavior during continuous charging is also stable. The maximum battery surface temperature at this time is 140 ° C ~ 2 10 ° C. In addition, in Comparative Example 2 -1 where the coating amount of lithium manganate was less than 27 g / cm2, although a high-capacity and high-output battery was obtained, the paper size was in accordance with China National Standard (CNS) A4. (210 X 297 public meals -------- ^-Γ " ^ | ^ pack -------- order --------- (please note the matters on the back of wtf first Refill transcript I) -50- 522593

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the Invention (49) However, the battery behavior during continuous charging will become fierce as the battery deforms. As a result, the battery surface temperature will exceed 30 (rc. On the contrary, in lithium manganate In Comparative Example 2_2 with a coating amount higher than 3 30 g / cm2, the battery behavior during continuous charging was stable, but as the output decreased, the result would not be suitable for use in electric vehicle batteries. Similarly, in Comparative Example 2_3 The amount of graphite in the positive electrode conductive material in the battery is less than 3% by weight, which results in a decrease in output. On the other hand, in the comparative example 2-4 battery in which the amount of graphite in the positive electrode conductive material is higher than 7% by weight, a high capacity can be obtained. And high output batteries, but the battery behavior during continuous charging will become fierce with the battery's shape. As a result, the surface temperature of the battery will exceed 300. Example 2 using graphite and amorphous carbon mixed in the positive electrode conductive material 2- Among the batteries of 6 to Examples 2_16_5, a battery with a high output L can be obtained. In the batteries of Examples 2 · 6 to 2-10 in which graphitized carbon black is used as the amorphous carbon, the active material is relatively positive. Example 2_8 ~ Example 2_10 of the secondary particle diameter of high-quality lithium manganate and the particle diameter of the conductive material graphite is 0.2 to 0.8, and higher output can be obtained. The particle diameter of the conductive material graphite is relatively In the batteries of Examples 2-7 in which the ratio of the secondary particle size of lithium manganate was lower than 0, the surface temperature of the battery during continuous charging was 20 (rc, slightly higher than that of the battery of Example H2-10. It was used for amorphous carbon. In the batteries of Example 2_u to Example 2-16-5 of acetylene carbon black, a higher output can be obtained, and the output maintenance rate after 100 charge and discharge is also high. The Li / Mn ratio of lithium manganate is within 0. .55 and above Examples 2_12 to 2-14, Examples 2 · 2-2 to Example m, Examples 2_16_2 to This paper size applies the Chinese National Standard (CNS) A4 (210 x 297 mm) 1 51- ---------.---------- ^ ---------- tPlease read the precautions on the back before filling in this page) 522593 Ministry of Economic Affairs Printed by the Intellectual Property Bureau employee consumer cooperative A7 B7 V. Description of the invention (50) The batteries of Example 2-16-4, Example 2-17-2 to Example 2-17-4 have a very high output maintenance rate. However, the Li / Mn ratio of lithium manganate is higher than .60 or more of the batteries of Example 2-15, Example 2-2-5, Example 2-1 6-5, and Example 2-17-5 will result in lower capacity, so It is found that the Li / Mn ratio is preferably in the range of 0.55 to 0.60. Examples 2-16, 2-16-2 to 2-16-5, and Example 2-16 where the negative electrode plate uses amorphous carbon. 17. Example 2-1 7-2 ~ Example 2-17-5 The battery can obtain extremely high output, and the extremely high output maintenance rate 'the minimum battery surface temperature during continuous charging. Therefore, the batteries of Examples 2-16, 1-16-2 to 2-16-5, 2-17, and 2-17-2 to 2-17-5 can be described as high-capacity, high-output, and Overall safe battery with good safety. As described above, the cylindrical lithium ion battery 12 of this embodiment is a battery with extremely smooth behavior and excellent safety when the battery is in an abnormal state. This type of high-capacity, high-output, and extremely safe battery is particularly suitable for EV power supplies. (Third implementation, Xiong Yu, Second, the third embodiment of using the present invention in a cylindrical bell ion battery for HEV will be described. In this embodiment, the positive electrode active material is positioned at a more suitable lithium manganese The preferred average particle size range of the double oxide and its primary particles. In addition, in the following embodiments of this embodiment, the same components as those in the first embodiment are given the same symbols, and the description is omitted, and only the differences are described. (Positive electrode) This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the note on the back; please fill in this page before the matter) Γ '· · 1 n · «1 · ϋ ϋ flu n * ϋ mni an · ϋ alal I = 0 -52 — 522593 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (51 The average particle size of primary particles of a positive electrode active material (hereinafter referred to as " Average primary particle diameter ") lithium manganate (Lii + xMn2.x04 or Li1 + xMn2.x.yAly04) powder below 2 μηι, flaky graphite of conductive materials, polyvinylidene fluoride (PVDF) as an adhesive, By weight ratio 8 5: 1 0: 5 Mix and add n_methyl-2 · ° ratio σ each ketone (NMP) to the dispersion solvent and knead it to form a slurry. Then apply this slurry to both sides of a foil with a thickness of 20 μm After that, after drying, pressing, and cutting, a thickness of 90 μm can be obtained. In the short acid warp, a spinel crystal structure is used and the composition ratio of Li to Mn (hereinafter referred to as "Li / Mn ratio") is 0.50 ~ 0 · 65. In addition, the manganese I clock system is synthesized by mixing and sintering appropriate salt and oxide, and the required Li / Mn ratio can be obtained by controlling the loading ratio of salt and manganese oxide. The lithium manganate used was randomly photographed at several positions using an electron microscope. From the photographed electron microscope, the primary particles were measured and the average number was calculated to confirm the average primary particle size. (Negative electrode) Negative electrode active material is 90 parts by mass of amorphous carbon powder. Polyvinylidene fluoride as a binder is added to 10 parts by mass of the negative electrode active material, and NMp is added as a dispersion solvent. To form a slurry after kneading. The material is coated on both sides of a rolled copper foil with a thickness of 10 μm. After drying, stamping, and cutting, a thickness of .7 () _ is obtained. Next, for the cylindrical lithium ion prepared according to this embodiment Dian 53-HIM -------- Order --------- f Please read the notice on the back before filling in this page} 522593 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Α7 Β7 V. Description of the Invention (52) An embodiment of the pool 20 will be described. A battery of a comparative example produced for comparison is also described. (Example 3-1) As shown in Table 5 below, in Example 3-1, the positive electrode active material used a Li / Mη ratio of 0.55, and the average primary particle diameter was 0.001 μm. The manganic acid was powdered (Lii.〇6Mn194〇4) to make a battery. Table 5 Primary particle size (nm) Active material composition Li / Mn ratio Example 3- 1 0.1 Lix.06Mn1.94O4 0.55 Example 3-2 0.5 Example 3-3 1.0 Example 3-4 2. 0 Example 3-5 0. 1 Lix.14Mn1.86O4 0. Β f Example 3-6 2. 0 Example 3-7 0. 1 LiMn9〇4 0.50 Example 3-8 L i 1 1 s Μη 1 .8 2.Q4 0.65 Example 3-9 L i τ π 1M π 1 r 7 A1 〇 τ 〇, 0.55 Example 3-1 0 2.0 Li! Π? Μπι «7 Αίο.τΟ, 0.55 ΛComparative Example 3 -1 0.05 Li1.〇6Mn1.94〇4 0.55 Comparison queue 3-2 2 .5 Comparative example 3-3 0.05 Lil.l4Mn1.86 ° 4 0.60 Than car delivery example 3-4 2.5 Comparative example 3-5 0.05 Li 1.03MΠ1. 87 Al〇.χ〇4 0.55 Comparison column 3-6 2. 5 (Examples 3-2 to 3-4) As shown in Table 5, in Examples 3-2 to 3-4 Except for the positive electrode active material, the battery was produced in the same manner as in Example 3 -1 except that the acidic bell powder with the average primary particle diameters of 0.5 μm and 1 · Ο μπι '2 · Ο μπι was used. (Examples 3-5, 3-6) As shown in Table 5 below, in Examples 3-5 and 3-6, the paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 male f ) nnn I Γ -J --I nn 1 nn «n ϋ ϋ n ϋ nn Order --------- line tl (Please read the note on the back before filling this page) -54 — 522593 A7 B7 V. Description of Invention (53 The positive electrode active material printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs uses a manganese acid (Lh.MMiiK ^ O4) powder with a Li / Mn ratio of 0.65, and the average particle size of its primary particles The battery was produced in the same manner as in Example 3-1 except that it was 0.1 μm in Example 3-5 and 20 μLm in Example 3-6. (Examples 3-7 to 3-10) As shown in Table 5, except in Examples 3-7, a manganese acid (LiMn2 04) powder having an average primary particle size of 0.1 μm and a Li / Mn ratio of 0.55 was used in Examples 3-8. , Li manganate (Lii.uMnmCu) powder with an average primary particle size of 0.ΐμπι and a Li / Mn ratio of 0.65 was used. In Examples 3 to 9, the average primary particle size was 0. 1 μm, and a part of η was substituted. Manganese with a Li / Mn ratio of 0.55 Lithium (1 ^ 1.031 ^ 111.87 eight 10.10) powder, in Example 3-10, lithium manganate (1 ^ 1.〇3% 111.87 Ba 1 (). 104) The battery was fabricated in the same manner as in Example 3-1 except for the powder. (Comparative Example 3-1 '3-2) As shown in Table 5 below, In Comparative Example 3-1 and Comparative I 3-2, the positive electrode active material was removed using ferric acid (Lh. 55 μm, primary particle average particle size, 2.5 μm, and Li / Mn ratio of 0.55). Except for MMni.wO4) powder, the battery was produced in the same manner as in Example 3-1. (Comparative Examples 3-3, 3-4) As shown in Table 5, below, in Comparative Examples 3-3 and Comparative Examples 3-4 In addition to the positive electrode active material, the primary particle average loose blade is used as the paper size. The Chinese national standard (CNS) A4 specification (210 X 297 mm) is applied. -55- {Please read the note on the back? Matters and then fill out this page) -1111111 522593 A7 B7 V. Description of the invention (54) Lithium manganate (LiKMMmwO4) powder with 0.05 μm, 2.5 μm, and Li / Mn ratio of 0.06, the rest are the same as in Example 3 "to make a battery. (Comparative Examples 3-5, 3-6) As shown in Table 5 below, in Comparative Examples 3 and 3-6, the average active particle size except for the positive electrode active material was 0. 05 μm and 2.5 μm, respectively, and Part of the Mη was replaced by lithium manganate (Lh.MMnuvAluOo powder) with a M / Mη ratio of 0.55, and the rest were made as in Example 3-1. ≪ Testing & Evaluation > The batteries in the examples and comparative examples were obtained. The current value (1C) capable of discharging for about 1 hour was used to control 4. IV constant voltage. After being charged for 3 hours and fully charged, the batteries were used at 10A, 30A, and 90A. The current value is discharged for 5 seconds respectively, and the battery voltage at the 5th second is measured. From this voltage, the straight line drawn by the current value reaches the current value (la) of 2 · 7 V, and the calculated output ((W) = Iax 2.7) Output measurement test. These measurements are performed in an environment of 25d: 2Ό. Table 6 shows the test results of the output measurement test. (Please read the precautions on the back before filling this page) iMW — Order --- ------ Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 g) 522593 A7 V. Description of the invention (55) Table 6 Rotating m. Example 3-1 930 Example 3-2 1 9T0 Example]- 3 9T0 Example 3-4 9T0 '~ Example 3-5-9T0 Example 3-6 6T0' ~ Example 3 J-8-7T0 '~ Example 3-8 8T0' ~ Passing on your j 3-9-9T〇 Passing on your j J-1 0 9Τ〇 Comparative example 3-1 8Τ〇 '~ Comparative example 3-2 8Τα Comparative example 3-3 Too Comparative life j 3-4 0 0 0 '~ Than k 3-5 8Τ〇 ~ Compare Θ 3-6 820 (Please read the back; please fill in this page before filling out this page) The Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs printed as shown in Table 5 and Table 6 It is shown that the positive electrode active material uses the lithium manganate lithium batteries of Examples 3-1 to 3-4 having a Li / Mn ratio of 0.5 5 and an average primary particle size of 0. to 2. 0 μm. The output according to the above measurement method is 93. ~ 96 ° w, in comparison, Comparative Example 3-1, in which the positive electrode active material uses lithium manganate having an average primary particle diameter of 0.0 5 μm, and the positive electrode active material uses lithium manganate having an average primary particle diameter of 2.5 μm. Example 3-2 The battery has an output of 900 to 820 W. Furthermore, the positive electrode active material uses lithium manganate with a Li / Mll ratio of 0.6 () and an average primary particle diameter of 0.1 to 2.0 μm. The battery exhibited output characteristics of 920 to 930 W. In contrast, the battery of Comparative Examples 3-3 and Comparative Examples 3-4 using lithium manganate having a primary particle average particle size of 2 μm as the positive electrode active material was 780-1800. 〇w output. Comparative Examples 3-7 using lithium manganate with a Li / Mn ratio of 0.50 and an average primary particle size of 0.1 μm, and a positive electrode active material 57-

-· N I n I ί ϋ n) I ϋ n n n n n I I 522593

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (56) In the case of the battery of Example 3-8 using lithium manganate with a Li / Mn ratio = 06 5 and an average primary particle size of 0 μm, It was found that the same phenomenon occurred in the output to some extent compared with the U / Mn ratio below 0.55 and 0.60. In addition, the same applies to the case where a portion of Mn is replaced by lithium manganate of A !, and the positive electrode active material uses lithium manganate having an average primary particle diameter of 0 2 2 m, and the batteries of Examples 3-9 to 3-10. The battery exhibited an output characteristic of 93 to 94 watts. On the other hand, the positive electrode active material used Comparative Example 3 of lithium manganate having an average primary particle diameter of 0.05 μm and 2,5 μm, and a battery of Comparative Examples 3-6. , It is the output of 820W. From the results of the above tests, it was found that the battery according to the embodiment of the positive electrode active material using lithium manganate having an average primary particle diameter in the range of 0.1 to 2.0 µm showed excellent output characteristics. Furthermore, in the battery of the embodiment, the battery having a Li / Mn ratio in the range of 0.555 to 0.60 has a higher output. This type of battery is effective in miniaturizing the size of the battery because it has a small internal impedance (response impedance) and high output even without widening the electrode area. (Fourth embodiment) Next, a fourth embodiment in which the present invention is applied to a cylindrical M-ion battery for HEV will be described. In this embodiment, the weight of the primary particle system of lithium manganese complex oxide is mainly determined from the viewpoint of safety. (Positive electrode) With respect to 90 parts by weight of lithium manganate (LiMn204) powder, conductive paper is added. The paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 g t) -------- ^- ------ Order --------- (Please read the precautions on the back before filling this page) 522593

V. Description of the invention (57) 5 parts by weight of flaky graphite powder of materials printed by employees of the Intellectual Property Bureau of the Ministry of Economic Affairs and consumer cooperatives; Methylpyrrolidone (NMP) is kneaded to form a slurry. This slurry was then coated on both sides of an aluminum foil having a thickness of 20 µm. After drying, pressing and cutting, the positive electrode can be obtained. Although lithium manganate can be synthesized by mixing manganese dioxide with lithium carbonate and sintering at a specific temperature, in order to adjust the particle size and specific surface area of lithium manganate, the particle size and sintering temperature of the manganese dioxide are changed. In addition, lithium manganate having a particle size of less than or equal to 0.01% and a specific surface area of 10 m2 / g or less is used. The weight percentage of particles with a particle size of 1'um or less is based on the weight of the dried lithium manganate weight A 'and the weight of the lithium manganate after filtering and filtering the residue using a sieve with a pore size μμm, according to (B / A) Calculated by χ 100. The specific surface area was determined by the BET one-point method for nitrogen adsorption. (Negative electrode) Negative electrode active material is N-methylpyrrolidine, which contains 90 parts by mass of polyvinylidene fluoride with a binder added to the amorphous carbon powder, and a dispersion solvent, After kneading, a slurry was formed. This slurry was coated on both sides of a rolled copper foil with a thickness of 0 μm. Then, after drying, punching and cutting, a negative electrode was obtained. Next, an embodiment of the cylindrical lithium ion battery 20 obtained according to this embodiment will be described. A battery of a comparative example produced for comparison is also described. (Example 4 -1 to 4-3) As shown in Table 7 below, in Examples 4-1 to 4-3, the original paper size was adapted to the Chinese National Standard (CNS) A4 specification (21Q x 297 meals) ) -------- Order --------- (Please read the precautions on the back before filling this page) -59- 522593

V. Description of the invention (58 Extremely active 1 ^ material is lithium manganate with a particle size of less than 1 μηι and a specific surface area of 0.4, 0.6, 1.0 m2 / g Table 7 ΈΜΛΤί Substance-Luxury 丨 I 4-2 ΤμϊηΙΓΤΙΕ? (Wt%) ns Compare you 丨 4-3 • 01 〇 Compare you IH compare you 丨 4-4 ratio 鲛 Example 4-S compare you丨 4.02.〇3 (Please read the unintentional matter on the back before filling in this page) Meeting (Comparative Example 4 -1 ~ 4_3) As shown in Table 7 below, in Comparative Example 4- 丨 ~ Comparative Example 4-3 In the example, except that the positive electrode active material uses a hard acid bell having a particle size of 丨 μηη or less and a weight of 0.02% 'and a specific surface area of 0.4, 0.6, and 1.0 m2 / g, respectively, the rest are the same as the examples 4 -1 Production of batteries. (Comparative Examples 4-4 to 4-6) As shown in Table 7 below, in Comparative Examples 4-4 to 4-6, except for the positive electrode active material, a particle size of 1 μΓη or less was used. The weight of the particles was 0.03%, and the specific surface areas were 0.4, 0.6, and 1.0 m2 / g of lithium manganate, and the rest were produced in the same manner as in Example 4-1. ≪ Testing & Evaluation > Follow Each of the prepared examples and comparative examples was charged using a current value of 3 hours (3 C) until the paper size of the book was adapted to the Chinese National Standard (CNS) A4 specification (210 X 297 g). ---------. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -60- 522593 A7 _____B7_________ V. Description of the invention (59) Overcharge test until the battery has an abnormal phenomenon, and measure the surface of the battery can 7 at this time The maximum temperature reached. The test results of the overcharge test shown in Table 8

-------- ^ — (Please read the note on the back of tf? Matters before filling out this page) Order printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs as shown in Table 8, Comparative Example 4 -1 ~ 4- The battery of 6 emits white smoke and reaches the southernmost temperature of about 4 0 C '. In contrast, Examples 4-1 to 4 using lithium manganate having a particle weight of 0. 0.001% and a particle size of 1 μm or less -3 battery, even when overcharged, the average unit volume area of lithium manganate and non-aqueous electrolyte will decrease, and because the heat dissipation of the deoxidation reaction will become smaller, white smoke will not be emitted, and the battery function will safely disappear. Furthermore, in Examples, the batteries of Examples 4-1 and 4-2 having a specific surface area of 0.6 m2 / g or less "because not only the interface area between the lithium manganate and the non-aqueous electrolyte solution can be reduced," but also the manganese acid can be suppressed. Lithium has a chain reaction with non-aqueous electrolyte, so it reaches a maximum temperature of 1000. 〇 The following are all very safe. Fifth Implementation Xiong Yi 1 Next, a fifth embodiment of the present invention is applied to a cylindrical money ion battery for HEV. In this implementation aspect, the lithium-manganese reoxidation is mainly determined from the viewpoint of maintaining high output for a long period of time. The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm-61- 522593 A7 B7). Printed by the Consumer Cooperative of the Property Bureau. 5. Description of the invention (weight of the primary particle system. (Positive electrode) 5 parts by weight of flaky graphite powder with conductive material added to 90 parts by weight of lithium manganate (LiMn ^ 4) powder. 5 parts by weight of polyvinylidene fluoride (PVDF), and an adhesive, and a dispersion solvent of N-fluorenylpyrrolidine_ (Li) 'was kneaded to form a slurry. This polymer was then coated on The aluminum with a thickness of 21 is dropped on both sides, and the positive electrode can be obtained after drying, stamping, and cutting. Although lithium manganate can be synthesized by using manganese dioxide and lithium carbonate and sintering at a specific temperature, but In order to adjust the particle size and specific surface area of lithium manganate, the particle size and sintering temperature of the manganese dioxide of the raw materials were changed, and the particle weight of 1 μm or less using particle technology was 〇〇 丨 0 /., 2 Q /. Or less And the specific surface area is 0.4m2 / g Above, lithium manganate of 3.0 m2 / g or less. As in the fourth embodiment, the weight percentage of particles having a particle size of 1 μm or less was calculated using the calculation formula of (B / A) χ 100, and the BET1 point of nitrogen adsorption was used. (Negative electrode) A negative electrode active material is formed by adding 10 parts by mass of polyvinylidene fluoride with a binder to 90 parts by mass of an amorphous carbon powder, and adding a dispersion solvent of N- Methylpyrrolidone is kneaded to form a slurry. This slurry is coated on both sides of a rolled copper foil with a thickness of 10 μm. After drying, stamping and cutting, a negative electrode is obtained. An example of the cylindrical lithium-ion battery 20 prepared by the embodiment will be described. In addition, it is also described for comparison purpose.

V uses the national standard of dry country (cns1 ^^ 21Qx 297: PJ --------- ^ —7 f * ------- subscribe · -------- line ^ | ^ · (Please read the precautions on the back before filling out this page) -62-522593 A7 B7 'V. Description of the invention (61) The battery of the comparative example (Examples 5-1 to 5-4) are shown in Table 9 below. As shown, in Examples 5-1 to 5-4, the extremely active material uses particles with a particle size of 1 μm or less, and the weights are 2.0%, 1.0%, 0.1 ° / 〇, 〇. 〇1%, and The specific surface area is 10 Claws 2 / ^ Lithium ferrate, which is used to make batteries. • -------- VI —-------- Order * ---- (Please read first please Please note on the back of this page to refill this page) Printed clothing by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (Examples 5-5 to 5-8) As shown in Table 9 below, in Examples 5-5 to 5 In -8, the positive electrode active material uses manganic acid with a particle size of 1 μπ! Or less, which weighs 0 '1% and has specific surface areas of 3.0m2 / g, 2.0m2 / g, and 0.6m2 / 0.4m2 / g, respectively. Except for lithium, the rest were made in the same manner as in Example 5 (Comparative Examples 5-1 to 5-2) As shown in Table 9, in Comparative Example ^ 丨 to Comparative Example 5.2, the depolarizing activity For the substance, the weight of particles with a particle size of 1 μηι or less, the amount of manganic acid with a specific surface area of 3.0%, 0.005% and a specific surface area of 〇m2 / g is used.

SJ Table 9 Particles below 1 μm fwt%) f Example 5 -1 2. 0 i7o ~ Example 5-2 1 .〇ΓΓδ '' — Example 5-3 0. 1 rrr ~ Will Example 5-4 0.01 rrr ~ — General Example 5-5 0. 1 η- Example 5-6 0. 1 27〇 · —Implementation Section 5-7 0. 1 〇7δ ~~ Example 5-8 0. 1 δ ~ Τ ~ — fct is more than you j 5 -1 3.0 Γ7ο ~ — compare Iraq j 5-2 0.005 ΓΓδ This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 63- 522593 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Making A7 B7 5. Except for the description of the invention (62), the rest were made as in Example 5-1. < Test and Evaluation > Secondly, for each battery prepared as described above, the battery state is a gradually discharged state. It is charged at 50 A for 10 seconds, and discharged at 100 A, 5 seconds, 50 A, 5 seconds of secondary power, the rest time is set to 5 seconds. The state of the battery is gradually charged in the second form. It uses 50 mAh to charge for 10 seconds and 5 seconds of secondary charging, while discharging uses 100 mAh for 5 seconds, and the rest time is set to 5 seconds. bell. The switching of this mode 1 and mode 2 is implemented when the upper and lower voltages reach 4.2V and the lower limit voltage is 3.0V. For the accelerated pulse charge-discharge cycle test, the ambient temperature was set to 50 °. 〇. After keeping the battery at a constant voltage of 4V, use 25A, 50A, and 100A to discharge, and measure the voltage at the 5th second. Trace this voltage to the current value and take a straight line. The current value (la) at the parent cross point is calculated by the calculation formula (Iax 3 0) (W). Before the output measurement system was subjected to a pulse charge-discharge cycle test (A (W)), and after performing a pulse charge-discharge cycle test (B (W)) of 100,000 times (number of discharges), the calculation formula (B / A ) χ 10〇, to obtain the pulse rotation maintenance rate (%). The results are shown in Table 10 below. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) --------- Ί! Cao (please read the intention on the back before filling this page). Order # · -64-522593 A7

V. Description of the invention (63) Table 10 出 ^ Maintenance rate (%, Example 5-1 Example 5-2 8 5 X Other example 5 Ί. 90 Knowing example 5-4 I-Η 7 Case 5-S 58 Case 5-G 7 2 Case 5-7 — 88 I Case 5-ft — 63 Case 5-1 — 4 8 Case 5-4 The Intellectual Property Bureau employee consumer cooperatives printed batteries of Comparative Example 5-1 and Comparative Example 5.2 with pulse output maintenance rates below 50 / 〇. In contrast, Examples% 1 to Examples $ _ $, The pulse output maintenance rate exceeds 50%, showing excellent pulse charge-discharge cycle characteristics. In addition, the batteries of Examples 5-5 and 5-8 have almost a pulse output maintenance rate of 7000 / 〇 or more. It shows superior pulse charge-discharge cycle characteristics. Compared with the battery of the car parent example 5 -1, because the particle size of the particle diameter of the acidic acid is less than 1 μm, it is 3% more 'so the adhesion between the positive electrode active materials It will be slightly weaker, and because the positive electrode active material will fall off during the pulse cycle test, a decrease in output will occur. In addition, the battery of Comparative Example 5-2, because The particle diameter of the acidic acid is less than 1 μηι, and the particle weight is too small. Therefore, because the chain ions cannot be inserted smoothly, the effect of reducing the discharge load applied to the overall positive electrode cannot be obtained, which reduces it. Pulse charge and discharge cycle characteristics. From the above results, it is known that the batteries of Examples 5-1 to 5-8 using lithium manganate with a particle size of 1 μm or less and a weight of 0.01% to 2% are superior pulse charge and discharge. Battery with cyclic characteristics. In this case, the paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm t) --------------------/ V ( Please read the precautions on the back before filling this page) Order ---- S. 65- 522593 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A. 5. Description of the invention (64): Use a specific surface area of 0.6m2 / In the battery of the embodiment where the lithium ferric acid is more than g and less than 20 m2 / g, the reaction area-compensation is increased, and the discharge reaction is performed, and it is expected that the discharge load applied to the overall electrode may be relaxed. Because: 1Prevention-the effect of destroying the structure of the positive electrode active material, because it is a pulse charge and discharge Batteries with excellent cycle characteristics. In this way, the cylindrical type ... Batteries at 2 ° C can maintain high output for a long period of time. It is particularly suitable for the power source of electric vehicles. In addition, in the above embodiment, although it is exemplified to delete A large secondary battery using a 'source', but the battery size and battery capacity of the present invention are not limited. However, the cylindrical lithium ion is-^ ^ ^ ^ injustice (the first embodiment looks like: ...) In this case, it has been confirmed that the effect of the present invention can be clearly exhibited for a battery having a battery capacity of about 3 rh. The capacity of the circle is around the secret ^ off the effect of the battery light. Therefore, it can be judged that it is best to use the battery capacity: in the second = = 'positive; the external terminal runs through the battery cover, and is separated from the positive and negative external terminals in the battery container. In another aspect, although a cylindrical battery is exemplified, in the above-mentioned implementation, the battery is not used, but the present invention does not limit the shape of the battery, and it may be an angular or other polygonal battery. Furthermore, in the above-mentioned embodiment, although a specific positive electrode active material is exemplified, the positive electrode active material used in the present invention is not special except for the requirements described in the scope of benefit = the active material can be inserted The material of the clock is best to be inserted in advance: Sufficient chain complex compound oxide, or a manganese paper ruler with a sunstone structure in another point & Cai Guan Jia Xian (CNS) A4 Na (210 --------- ^ Clothing ------- Order · --- (Please read the > i notice on the back before filling in this page)

S 522593 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 V. Description of the invention (65) Lithium acid, or a material in which some manganese or lithium in the crystal is substituted or doped with other elements. In general, although lithium manganate can be synthesized by mixing appropriate lithium salts with manganese dioxide and sintering, it can also be obtained by controlling the filling ratio of salt and manganese oxide. Needed two. Furthermore, in the third embodiment, lithium manganate represented by W ^ Η Li1 + xMn2.x〇4 or a part of manganese in the chemical formula is an example of lithium manganate +, of course, such a cathode is active. Also = for other batteries (-, 2nd, 4th, 5th). Therefore, the present invention is not limited to the ferric acid having the above-mentioned chemical formula, and can be applied to a lithium manganate shown in another chemical formula in which a sufficient amount is inserted in advance. In addition, instead of A1, it can also be obtained through c0, Ni, F rm, Fe, Cu, Cr,

Mg 'Zn, V, Ga, B, and F are presently the case of lithium manganate (Li1 + xMn2 | yMy〇4) substituted or doped with metal element M' of the orthodox temple. In addition, in the above embodiment, the specific negative electrode active material is exemplified, and there are no particular restrictions on the others except for the requirements described in the scope of the patent application to be described later. Sin, such as === ink, artificial graphite materials, coke, crystal, etc. The particle shape, such as scaly, spherical, fibrous, and massive #, is not particularly limited. In the description of the material description, 'Although the example of the insulation coating belongs to the tape with the substrate consisting of hydrazine fe, and the adhesive coated on one side is an example of the tape, ^ methacrylic acid is taken from the two A., Ding Dan It is also possible to use a base material such as…, polyethylene, etc. and its single or double sides coated with acrylic adhesive such as hexamethyl acrylic acid or acrylic acid butyrate III 的 IIIIII ί fv-ιί ^ I * 111 — — — — tr --------- 线 # · (Please read the back of the page first; the meaning of the matter before filling this page) This paper size applies to China Standard (CNS) ^ ji (21_J729_f) 522593 Printed by A7 of the Consumer Property Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs A7 ___ ___________ B7_ V. Description of the invention (66) Adhesive tape, or composed of polyolefin or polyimide without an adhesive In addition, in the above embodiment, the electrolyte solution is exemplified by a mixed solution of ethylene carbonate, stone antimony, and a volume ratio of diethyl carbonate of 1: 1: 1. Dissolving lithium hexafluoride in medium to 1 mol / liter, but there are no special restrictions on the electrolyte in this hair month, and it can be used Commonly used. In other words, the non-aqueous electrolyte can be an electrolyte in which a general bell salt is used as an electrolyte and is dissolved in an organic solvent. The lithium salt or organic solvent used is not particularly limited. For example, the electrolyte can be used

LiC104 ^ LiAsF6 > LiPF6. LiBF4. LiB (C6H5) 4 > CH3S〇3Li, CFsSC ^ Li, etc., or a mixture thereof. Non-aqueous electrolyte organic solvents can be used: propyl carbonate, ethylene carbonate ', 2 • dioxoethane, diethoxyethane, γ-butenecole, and 1 TJ 円 tetrafuran, 1,3-dioxolane, 4-fluorenyl ", 3-dioxolane, diethyl ether, cyclobutane, fluorenylcyclobutane, acetonitrile, propionitrile, etc., or two or more of these Mixed solvents. There are no particular restrictions on the mixing and blending ratios. In addition, in the above embodiment, the adhesive is exemplified by polyvinylidene fluoride. However, the present invention is not limited to this. Teflon 'polyethylene can also be used. , Polystyrene, polybutadiene, butyl rubber, nitro rubber, styrene / butadiene rubber, polyvulcanized rubber, cellulose, cyanoethyl oryzanol, polyvinyl alcohol, various latex, acrylic Fine, fluorinated ethylene, polyvinylidene fluoride, fluorinated propylene, fluorinated propylene and other polymers, as well as mixtures, etc. Λ [Illustration of Symbols] This paper size applies to Chinese National Standard (CNS) A4 specifications (210 X 297 mm) -------- ^ -------- Order · -------- (Please read the i sound on the back of tt? Matters before filling in this > 522593 A7 B7 V. Description of the invention (67) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 2 3 4 5 6 7 8 9 10 11 12 13 14 20 101 10Γ 102 103 103! 104 105 106 107 108 109 110 111 114 Shaft core positive lead, negative lead, positive current collector ring, negative current collector ring, wound battery pack, negative electrode, positive plate, air guide, crack, valve cover, case, cap, valve, pusher, cylindrical lithium ion battery, positive external terminal, negative external Terminal cap body First ceramic washer Second ceramic washer Battery cover Battery container winding group Flange Insulation coated conductive sheet crack valve shaft metal washer (Please close the back first; please note this page before filling in this page) Base — This paper Standards apply to China National Standard (CNS) A4 specifications (210 X 297 mm) 522593 A7 _B7 V. Description of the invention (68) 115 Perfusion α 116 〇ring 120 Cylindrical lithium ion battery W2 Positive active material mixture layer W3 Rolling Copper foil W4 Negative electrode active material mixture layer W5 Polyethylene separator — — — — — — — — -I -------- Order · -------- Η -f \ (Please read the notes on the back of this page and then fill in) Ministry of Economic Affairs Intellectual Property Office employees consumer cooperatives printed in this paper scale applicable Chinese National Standard (CNS) A4 size (210 X 297 male t) -70-

Claims (1)

522593 A8 B8 C8 Scope of patent application Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economics 1. A non-aqueous electrolyte secondary battery, characterized in that it contains lithium that is formed from primary particle aggregates, and lithium that is composed of the secondary particles Positive electrode active material of manganese multiple oxide and conductive material. The positive electrode active material mixture of 4 positive electrode active materials is applied to the positive electrode on both sides of the T-shaped current collector in an approximately equal amount. “Negative electrode” A positive electrode and a negative electrode are wound through a separator to form an electrode winding group, and the electrode winding group is stored in a non-aqueous electrolyte secondary in a battery container having an internal pressure opening mechanism that releases the internal pressure by a specific pressure. Batteries; wherein the average particle size of the lithium manganese re-oxidized primary particles is in the range of 0 丨 μιη ~ 2 μιη 2 · As in the non-aqueous electrolyte secondary battery of the first patent application scope, the bell is re-oxidized The Li / Mii composition ratio of the product is in the range of 0.5 to 5 · 0. 3. The non-aqueous electrolyte secondary battery according to item 1 of the scope of patent application, wherein the M complex oxide is represented by the chemical formula Ui + xMn2-x〇4. 4 · If the non-aqueous electrolyte secondary battery in item 1 of the patent application scope, the M violent complex oxide is a part of the chemical formula Ul + xMn2-x〇4, which is replaced or doped with other metal elements. 5. If the non-aqueous electrolyte secondary battery of item 1 of the scope of patent application, the lithium-manganese complex oxide has an average coating on one side of the electrode body of 80 g / m2 to 160 g / m2; and the Cathode active material 60 shows its weight and activity (please read the precautions on the back before f page) m, Tai Chi · ♦ This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 522593 A8 B8 C8 D8 Patent application scope The amount of conductive material contained in the agent is in the range of 8% to 16% by weight. 6. If the non-aqueous electrolyte secondary battery of item 1 of the patent application scope, wherein the lithium-manganese complex oxide has an average coating amount on one side of the electrode body of 270 g / m2 to 3 30 g / m2; The amount of the conductive material contained in the positive electrode active material active agent is in a range of 3% to 7% by weight. 7. The non-aqueous electrolyte secondary battery as claimed in claim 5, wherein the conductive material is a mixture of graphite and amorphous carbon. 8. The non-aqueous electrolyte secondary battery according to item 7 of the application, wherein the average particle diameter of the graphite is in a range of 0.2 to 0.8 times the average particle diameter of the secondary particles. 9. The non-aqueous electrolyte secondary battery according to item 7 of the patent application, wherein the amorphous carbon is acetylene carbon black. 10. The non-aqueous electrolyte secondary battery according to item 8 of the scope of patent application, wherein the amorphous carbon is acetylene carbon black. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 11. If the non-aqueous electrolyte secondary battery of item 6 of the patent application scope, the Li / Mn composition ratio of the lithium manganese complex oxide is in the range of 0.55 to 0.60. 12. The non-aqueous electrolyte secondary battery according to item 6 of the patent application, wherein the active material of the negative electrode is amorphous carbon. 1 3. If the non-aqueous electrolyte secondary battery in item 3 of the scope of patent application, the paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 522593 The scope of patent application for the production of A8 B8 C8 D8 is that the lithium manganese complex oxide system has a particle size of 1 μm or less and a weight of 0. 01% or less. 14. The non-aqueous electrolyte secondary battery according to item 13 of the patent application scope, wherein the specific surface area of the lithium manganese complex oxide is 0.6 m2 / g or less. 15. The non-aqueous electrolyte secondary battery according to item 3 of the scope of patent application, wherein the weight of the particles having a particle diameter of 1 μm or less based on the complex oxide series is in the range of 0.01% to 2%. 1 6 · The non-aqueous electrolyte secondary battery according to item 15 of the scope of patent application, wherein the lithium-manganese complex oxide has a specific surface area of 0.6 m2 / g to 2.0 m2 / g 〇 1 7. The non-aqueous electrolyte secondary battery according to the item, wherein the weight of the particles having a particle diameter of 1 μm or less based on the complex oxide system is 0.0 1% or less. 18 · The non-aqueous electrolyte secondary battery according to item 17 of the scope of patent application, wherein the specific surface area of the lithium complex oxide is 0.6 m 2 / g or less. 19 · The non-aqueous electrolyte secondary battery according to item 4 of the scope of patent application, wherein the weight of the lithium manganese multiple oxide-based particles having a particle size of 1 μm or less is within a range of 0.01% to 2%. 2 0. The non-aqueous electrolyte secondary battery according to item 19 of the scope of patent application, wherein the specific surface area of the lithium-manganese complex oxide is 0 · 6m2 / g ~ 2 · 0m2 / g. 〇 This paper size applies Chinese national standards ( CNS) A4 size (210 X 297 mm) Please read the notes on the back f